Natural resin formulations

ABSTRACT

This invention is directed to a method of preparing a natural resin by liquefying wood, bark, forest residues, wood industry residues, or other biomass using rapid destructive distillation (fast pyrolysis). Fast pyrolysis produces both vapors and char from biomass, and following removal of the char from the product vapors, a liquid pitch product is recovered and processed by distillation, evaporation, or a combination thereof, in order to obtain a natural resin which may be in either liquid or solid form. The natural resin comprises a total phenolic content from about 30% to about 80% (w/w), and is a highly-reactive ligninic compound that has been found to be suitable for use within resin formulations without requiring any further extraction or fractionation procedures. Resins comprising up to 60% natural resin have been prepared and tested in board production and found to exhibit similar properties associated with commercially available resins. The natural resin may substitute for phenol, or for both phenol and formaldehyde within phenol-containing resins. Similarly, the natural resin can replace a substantial part of the components within urea-containing resins.

This application is the National Stage of International ApplicationPCT/CA00/00868, filed on Jul. 28, 2000, which is a continuation-in-partof U.S. application Ser. No. 09/364,610, filed Jul. 29, 1999, now U.S.Pat. No. 6,326,461.

The present invention relates to the production and use of a naturalresin, derived from wood, bark, forest residues, wood industry residuesand other biomass materials using destructive distillation, its use asan adhesive in the manufacture of manufactured wood products, and itsuse in other resin formulations.

BACKGROUND OF THE INVENTION

“Resin” is a generic term used to describe both natural and syntheticglues which derive their adhesive properties from their inherent abilityto polymerize in a consistent and predictable fashion. The vast majorityof modern industrial resins are synthetic, and are normally derived frompetroleum feedstocks. Two of the most important classes of syntheticresins, in terms of production volume and total sales are phenolformaldehyde (P/F) and urea formaldehyde (U/F) resins. In both cases,the principal market application is for use as a glue binder in man-madewood products.

Phenol formaldehyde (P/F) resin, because of its resistance to moisture,has a particular value in external (outdoor) or damp environments. It istherefore, the leading adhesive used for the manufacture of plywood,oriented strand board (OSB) and wafer board (Sellers, 1996). P/F resinsare also widely used in laminates, insulation, foundry materials,moulding compounds, abrasives and friction materials for thetransportation industry (ie., clutch facings, disk facings andtransmission components). As its name suggests, the principalingredients in P/F adhesives are phenol and formaldehyde. However, thefinished product is actually a mixture of P/F, caustic, and water,.Assorted fillers, extenders and dispersion agents may then be added forspecific adhesive applications.

The formaldehyde ingredient in P/F resin is derived from methanol,normally produced from natural gas. The phenol ingredient is typicallymanufactured from benzene and propylene via a cumene intermediate. Inaddition to P/F adhesive manufacture, phenol is used in the manufactureof other important products, for example, Bisphenol A and Caprolactam.Bisphenol A is a principal component in polycarbonates used inautomotive parts, compact discs and computer discs, and Caprolactam is araw material for Nylon 6, used within stain resistant carpets.

When mixed together in water and with caustic added as a catalyst,phenol and formaldehyde undergo a condensation reaction to form eitherortho- or para-methylolphenol. The resultant PF resin, as shipped tomarket, is a dark brown liquid which is polymerized and cross-linked toan intermediate degree. It is then cured in the final board, laminate orother product without catalyst simply with the addition of heat at whichtime the final polymerization and cross-linking take place viacondensation reactions. The release of free formaldehyde during theresin manufacture and resin use stages is a concern from a health andsafety perspective. Furthermore, the costs associated with formaldehydeproduction have increased and there is a need in the art for alternativematerials for use as wood adhesives and binders.

One alternative for phenol that has been considered are lignins whichhave been recovered from wood, wood residues, bark, bagasse and otherbiomass via industrial or experimental processes Natural lignin (i.e.the polymer which occurs in nature which holds wood and bark fibrestogether and gives wood its strength) and P/F formaldehyde resins arestructurally very similar. Lignin is a random network polymer with avariety of linkages, based on phenyl propane units. Lignin-basedadhesive formulations have been tested for use within plywood, particleboard and fibre board manufacture. The addition of polymeric lignin toP/F formulations has been found to prematurely gel the P/F resin therebyreducing shelf life, limiting permeation of the lignin-P/F resin intothe wood and producing an inferior mechanical bond (Kelley 1997). It isimportant to note that lignins which are isolated and recovered frombiomass, and which have been tested in resin formulations, are notidentical to the natural lignin present in the original biomass, but arealtered somewhat by the recovery process. Some examples of recoveredlignins which have been tested in PF resin formulations are Kraftlignin, lignosulphonates, Alcell™, Organocell™, pyrolytic lignin andnatural resin of the present invention.

Pyrolysis of lignin has been considered as a potential approach toupgrading lignin to more usable phenolic type resins. While relativelymild thermal or thermo-catalytic processing at low pressures can be usedto break the lignin macromolecules into smaller macromolecules, ligninsegments and monomeric chemicals, such procedures may cause condensationreactions producing highly condensed structures such as char and tar,rather than depolymerized lignin fragments or monomeric chemicals.

A further alternative for the production of phenolic compounds involvesuse of pyrolytic pitch oils produced in the rapid destructivedistillation (fast pyrolysis) of wood and other biomass. Fast pyrolysiscan be achieved by rapid heat transfer to the feed material, by rapidremoval of the product via a vacuum, or by a combination of rapid heattransfer and pyrolysis under vacuum. These pitch oils are comprised of acomplex mixture of compounds including phenolic compounds, guaiacol,syringol and para substituted derivatives, carbohydrate fragments,polyols, organic acids, formaldehyde, acetaldehyde, furfuraldehyde andother oligomeric products (Pakdel et al 1996). However, wood-derivedlignin and lignin-rich pyrolytic bio-oils have lacked consistency andhave exhibited inferior properties when compared withphenol-formaldehyde resins (Chum et al. 1989; Scott 1988; Himmelblau1997; Kelley et al., 1997).

Due to the complexity of pyrolytically-derived bio-oils, furtherprocessing is required in order to obtain suitable fractions useable asa replacement for phenol, or to be considered as an extender forpetroleum-derived phenol within P/F resin formulations. Typically thephenolic derived from pyrolysis oils requires separation prior to use inorder to remove impurities. One such method involves water extraction ofthe whole-oil, followed by precipitation and centrifugation orfiltration and drying of the non-aqueous fraction to prepare a“pyrolytic lignin” fraction (Scott 1988). However, adhesive formulationsprepared using pyrolytic lignin were found to be inferior to P/F resinformulations in both colour and odour, and required long press times inorder to avoid de-lamination of waferboards. Tests indicated that noneof the pyrolytic lignin samples meet the internal bond (IB) testrequirement (Scott 1988, see pp. 91-92).

In U.S. Pat. No. 4,209,647 (Jun. 24, 1980) a fractionation method forthe preparation of a phenol-enriched pyrolytic oil is disclosed whichinvolved a multistep process that selectively solubilized neutralphenols, and organic acids of the whole-oil with NaOH followed byextraction with methylene chloride. However, this multistep process iscostly, labourious, time consuming and involves the use of volatilesolvents that are known to be health threatening.

Another fractionation method involves adding ethyl acetate to whole-oilpitch to produce ethyl acetate soluble and insoluble fractions. Theethyl soluble fraction is then isolated and the ethyl acetate evaporatedto isolate a fraction containing phenolic and neutrals (P/N) derivedfrom the pyrolytic oil (Chum et al. 1989, U.S. Pat. No. 4,942,269, Jul.17, 1990, and U.S. Pat. No. 5,235,021, Aug. 10, 1993). Preliminaryresults with the P/N fractions revealed that fractionated pyrolytic oilscould be used within P/F resin compositions, as P/N containing resinsexhibited equivalent gel times as noted for P/F resins. However, thefractionation protocol is not suitable for industrial scale production,nor is this process cost effective for the preparation of alternativecomponents for use within P/F resins at a commercial scale (Kelley etal., 1997).

All of the process disclosed within the prior art as outlined aboveinvolve the extraction of a phenol-enhanced fraction from the wholepyrolytic oil product using complex protocols involving precipitation,followed by centrifugation or filtration, or the use of solvents andalkali. None of the prior art discloses methods for the production of abio-oil which is readily prepared from the whole pyrolytic oil or thatexhibits properties suitable for adhesive use. Furthermore, the priorart does not disclose methods directed at producing a fraction ofbio-oil suitable for adhesive use, yet that is simple to produce andthat does not require any solvent extraction.

It is an object of the invention to overcome disadvantages of the priorart.

The above object is met by the combinations of features of the mainclaims, the sub-claims disclose further advantageous embodiments of theinvention.

SUMMARY OF THE INVENTION

The present invention relates to the production and use of a naturalresin, a highly reactive ligninic product, derived from wood, bark andother biomass residues using rapid destructive distillation, forexample. fast pyrolysis. Specifically, the natural resins (NR) of thisinvention are obtained from the fast pyrolysis of wood products. The NRis obtained from a ligninic fraction of the liquid pitch productproduced from fast pyrolysis of biomass.

By the processes of the present invention, there is no need to extract aphenol enhanced portion using solvents, water induced solids separation,or alkali. Rather the NR of this invention may be produced from aselected product fraction of the whole-oil obtained from the pyrolyticprocess, or from the whole-oil product. The whole-oil, selected productfraction, or a combination thereof, is processed in a manner thatreduces non-resin components including odorous components and acids inorder to produce NR. Such a processing step involvesdistillation/evaporation.

The natural resins (NR) of the present invention can be used as asubstitute for some of the phenol in phenol/formaldehyde, phenol ureaformaldehyde, and phenol melamine urea formaldehyde resins used asadhesives in the manufacture of wood products, or the NR can be used asa substitute of some of the phenol and some the formaldehyde componentsof phenol-containing formaldehyde resins, for example industrialphenol-formaldehyde resins. Furthermore, the NR of this invention can beused as a substitute within urea formaldehyde resins, and melamine ureaformaldehyde, and related resins. The natural resins of the presentinvention can be used as a substitute for either some of the phenolcomponent of a phenol-containing formaldehyde resin or for both thephenol and formaldehyde components of the resin, or as a substitutewithin urea formaldehyde type resins.

The natural resins of the present invention exhibit high reactivity dueto the presence of a high number of active sites for binding and crosslinking during polymerization.

According to the present invention there is provided a method ofpreparing a natural resin (NR) comprising:

-   -   i) thermally converting a suitable biomass via rapid destructive        distillation in order to produce vapours and char;    -   ii) removing the char from the vapours;    -   iii) recovering the vapours to produce a liquid pitch product;    -   iv) processing the liquid product using distillation/evaporation        to produce the NR.

The present invention embraces the above method, wherein the step ofprocessing uses the liquid product obtained from a primary recoveryunit, a secondary recovery unit, or a combination thereof.

This invention also pertains to the above method wherein the step ofprocessing comprises the addition of water to the NR to produce an NRwith reduced viscosity.

This invention relates to the above method wherein the step ofprocessing comprises removing essentially all of the water content ofthe NR to produce a solid NR.

Furthermore, the present invention relates to the method as definedabove wherein the step of processing comprises pretreating the liquidproduct prior to distillation/evaporation. Preferably, the step ofpretreating comprises a water wash to reduce viscosity, improveflowability into downstream equipment and enhance the removal ofnon-resin components.

This invention is also directed to a natural resin (NR) characterized bycomprising a water content up to about 20%, pH of about 2.0 to about5.0, and acids content from about 0.1 to about 5 (dry wt %) and aviscosity of about 6 to about 130 cST (@70° C.) for liquid NR, or the NRmay be solid NR.

This invention is also directed to a resin composition that comprisesthe NR as defined above. Furthermore, this invention is directed to aresin composition comprising NR from about 1% to about 40% (w/w) of theresin composition.

This invention is also directed to a resin composition as defined abovecomprising a phenol-containing or urea containing formaldehyde resin.Furthermore, this invention relates to a resin composition as definedabove wherein the phenol-containing or urea-containing formaldehyderesin is selected from the group consisting of phenol formaldehyde, ureaformaldehyde, phenol melamine urea formaldehyde, melamine ureaformaldehyde, and phenol urea formaldehyde.

This invention also relates to a resin composition as defined abovewherein the NR comprises from about 20 to about 40% (w/w) of the resincomposition. Furthermore, the resin composition of this invention mayfurther be characterized in that a portion of the formaldehyde, withinthe formaldehyde-phenol resin is replaced with NR, and wherein the NRreplaces up to about 50% of the formaldehyde content of the resin.Preferably the adhesive composition comprises a formaldehyde:phenolratio from about 1.2:1 to about 3:1. This invention is also directed toa resin composition wherein a portion of the phenol within aformaldehyde phenol resin is replaced with NR.

This invention also relates to mixtures of natural resin, comprisingwhole-oil and fractions of whole-oil. Furthermore, this invention isdirected to adhesive compositions and industrial resins comprisingnatural resin mixtures. This invention also includes phenol-containingformaldehyde resins comprising natural resin, or natural resin mixturesthat replaces up to 100% of the phenol content of the phenol-containingresin.

This invention also embraces a wood product prepared using the adhesivecompositions as defined above. Preferably, the wood product is selectedfrom the group consisting of laminated wood, plywood, particle board,high density particle board, oriented strand board, medium density fiberboard, hardboard or wafer board. Furthermore, the wood product preparedusing the adhesive composition of this invention is used for exterior,interior or both interior and exterior applications.

This invention also pertains to industrial phenol formaldehyde resinproducts including mouldings, linings, insulation, foundry materials,brake linings, grit binders, for example to be used within abrasivessuch as sand paper, and the like.

Use of a fast pyrolysis process to produce the bio-oil is beneficial inthat the fast pyrolysis process depolymerizes and homogenizes thenatural glue component of wood, that being lignin, while at the sametime other constituents are also depolymerized including cellulose andhemicellulose. The beneficial components are enhanced within NRfollowing the step of distillation/evaporation The yield of NR,depending upon the biomass feedstock and the fraction of bio-oil usedfor NR preparation via distillation/evaporation, varies from 15-60% ofthe feedstock and exhibits properties that are useful within, forexample, phenol-containing, or urea-containing formaldehyde resincompositions. The natural resin so produced can be substituted for someof the phenol and formaldehyde, content within phenol-containingformaldehyde resins, and such formulations meet or exceed current phenolformaldehyde resin industry specifications. Furthermore, NR cansubstitute for some of the formaldehyde within urea-containingformaldehyde resins. With removal of the organic acids, the NR cancompletely substitute for the phenol content in phenol resins, and canalso be used within urea-containing formaldehyde resin formulations.

This summary of the invention does not necessarily describe allnecessary features of the invention but that the invention may alsoreside in a sub-combination of the described features.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features of the invention will become more apparent fromthe following description in which reference is made to the appendeddrawings wherein:

FIG. 1 shows a schematic of a rapid destructive distillation system, forexample, which is not to be considered limiting in any manner, fastpyrolysis.

FIG. 2 shows an aspect of an embodiment of the present inventioncomprising a flow chart outlining the production of several naturalresins. FIG. 2 (A) is a schematic showing one of several possiblemethods for the production of NR60D-WH. FIG. 2 (B) shows one of severalschematics for the production of NR80D-WH. 1° C. and 2° C. refer to theliquid products obtained from the primary and secondary recovery unit,respectively.

FIG. 3 shows an aspect of an embodiment of the present inventioncomprising a flow chart outlining the production of several naturalresins. The schematic outlines the one of the possible methods for theproduction of MNRP-1H and NR60D-2H. 1° C. and 2° C. refer to the liquidproducts obtained from the primary and secondary recovery unit,respectively.

FIG. 4 shows an aspect of an embodiment of the present inventioncomprising a flow chart outlining the production of several naturalresins. The schematic outlines the one of the possible methods for theproduction of NR60D-1H and NR60D-2H. 1° C. and 2° C. refer to the liquidproducts obtained from the primary and secondary recovery unit,respectively.

FIG. 5 shows an aspect of an embodiment of the present inventioncomprising a flow chart outlining the production of several naturalresins. The schematic outlines the one of the possible methods for theproduction of NR60D-1H, NR60D-2H, and NR60D-WH. 1° C. and 2° C. refer tothe liquid products obtained from the primary and secondary recoveryunit, respectively.

DESCRIPTION OF PREFERRED EMBODIMENT

The present invention relates to the production and use of a naturalresin, a highly reactive ligninic product, derived from wood bark andother biomass residues using rapid destructive distillation, forexample, fast pyrolysis.

The following description is of a preferred embodiment by way of exampleonly and without limitation to the combination of features necessary forcarrying the invention into effect.

By “bio-oil”, “whole-oil” or “light pitch” it is meant the whole liquidfraction obtained following rapid destructive distillation, for examplefast pyrolysis, of wood or other biomass, including for example,softwood, hardwood, bark, or agricultural residues. Fast pyrolysis canbe achieved by rapid heat transfer to the feed material, by rapidremoval of the product via a vacuum, or by a combination of rapid heattransfer and pyrolysis under vacuum. The whole oil is obtained from theproduct vapour which is produced along with char following pyrolysis.Upon removal of the char the product vapour is condensed and collectedwithin one or more recovery units, for example one or more condenserswhich may be linked in series. Whole-oil, bi-oil or light pitch refersto the combination of the condensed products obtained from all of therecovery units. Whole oil, or a fraction of the whole-oil which canobtained from at least one of the recovery units as described below, ora combination of whole oil and a selected product fraction, or acombination of different selected product fractions, may be used as afeedstock for further processing according to the methods of the presentinvention in order to produce a natural resin. By “oil feedstock”, it ismeant a whole-oil or light-pitch, or a selected product fraction of thewhole oil or light pitch, or a combination thereof, that may be used forfurther processing as described herein.

By “selected product fraction”, or “fraction of the whole oil” it ismeant a fraction of the liquid product that is obtained from a productvapour following removal of char and condensation. For example, which isnot to be considered limiting in any manner, the selected productfraction may comprise the liquid product obtained from at least onerecovery unit, for example a primary recovery unit, a secondary recoveryunit, or a combination thereof. The selected product fraction may beused as a feedstock for further processing in order to produce an NR ofthe present invention, or it may be combined with a whole-oil or anotherselected product fraction to produce an NR.

By “recovery unit” it is meant a device that collects product vapoursproduced during pyrolysis. A recovery unit may include, but is notlimited to, a condenser means which cools and collects a liquid productfrom the product vapour as is known within the art. A recovery unit mayalso include de-misters, fiber filter beds or other devices used withinthe art to collect the liquid product from the product vapour. Arecovery unit may comprise one or more components, for example, one ormore condensers, which are typically linked in series.

By “distillation/evaporation” it is meant the processing of a whole-oiloir light pitch, or a selected product fraction, via non-destructivetechniques in order to drive off water, acids, for example, but notlimited to acetic acid, odorous and non-resin components or acombination thereof. The product of this step may be used as an NR, orit may be further processed, for example but not limited to, theaddition of water, in order to produce an NR. The step ofdistillation/evaporation provides for a controlled polymerization of thefeedstock and maintains reactive lignin sites in the product. Typically,the non-destructive techniques for distillation/evaporation include, butare not limited to:

-   -   evaporation, for example wipe film evaporation (W.F.E),        roto-evaporation, agitated film evaporation, short tube vertical        evaporation long tube horizontal evaporation, or other        evaporation techniques known within the art;    -   distillation, for example, but not limited to vacuum        distillation;    -   heat exchange, for example, but not limited to, falling film        exchanger, scraped surface exchanger, or Teflon® heat exchanger;    -   water treatment, for example, but not limited to the addition of        water, or a water-base solution comprising for example NaOH or        KOH, at a temperature of from about 40° C. to about 60° C.;        or other physical or chemical process which removes, evaporates,        isolates or otherwise drives off acids, volatiles, water and        other light components which are less effective in terms of        resin properties and which contain odorous components. Such        techniques are known to one of skill in the art, see for example        Perry's Chemical Engineers Handbook (6th Edition, R. H. Perry        and D. Green eds, 1984; which is incorporated by reference).

Processing of the feedstock by distillation/evaporation can becontrolled to produce an optimized degree of cross-linking orpolymerization. With out intending to limit the present invention in anymanner, NR can be prepared by heating the oil feedstock under vacuum toa temperature which is sufficient to devolatilize odorous and non-resincomponents. If a liquid NR is to be produced, the water content of theoil feedstock may monitored during distillation/evaporation to determinethe degree of devolatilization so that a final water content of theintermediate liquid NR product is between about 1 and about 10 wt % isobtained. Preferably the final water content of the intermediate liquidNR product is between about 1 and about 5 wt %. The moisture content ofthe intermediate NR product is further adjusted to produce the finalliquid NR product. For solid NR the water content is from about 1 toabout 8 wt %, however, this NR is in a more polymerized state. Thedegree of polymerization may be controlled by the amount of heat usedduring distillation/evaporation, the amount of time the whole-oil orfraction thereof is subjected to the heat, or a combination thereof.Typically, the more heat or the longer the feedstock is subjected to theheat, or both more heat and longer exposure to heat, results in a moreviscous product with a higher average molecular weight than thefeedstock. Furthermore, it has been observed that the step ofdistillation/evaporation increases the proportion of phenolic-enhancercomponents within the NR.

The natural resin (NR) of this invention may comprise a whole-oilproduct that has undergone a controlled polymerization throughdistillation/evaporation, or it may include a selected product fractionof the whole liquid product that has been processed throughdistillation/evaporation, or it may include a combination of thewhole-oil and selected product fraction that has been subjected todistillation/evaporation. NR includes both a liquid NR, for exampleNR60, as well as a solid NR, for example MNRP. Liquid NR's may span arange of viscosities and comprising a range of phenolic contents asdescribed herein. Furthermore, the oil feedstock may be pretreated priorto the step of distillation/evaporation, and it may be further processedfollowing distillation/evaporation.

The oil feedstock is preferably produced from the destructivedistillation of wood, using for example, but not limited to fastpyrolysis. However, other processes that are able to liquefy wood mayalso be used to prepare an oil feedstock from which a NR may beobtained. Fast pyrolysis can be achieved by rapid heat transfer to thefeed material, by rapid removal of the product via a vacuum, or by acombination of rapid heat transfer and pyrolysis under vacuum. The oilfeedstock obtained from fast pyrolysis is primarily comprised ofdepolymerized lignin and other reactive components including phenolicswhich provide an array of active sites for binding and cross linkingwithin the NR formulations of the present invention. Non-reactivecomponents are removed during the preparation of the NR, including thedistillation/evaporation of the whole-oil, selected product fraction, ora combination thereof, or other steps for pretreating the oil feedstock,for example water washing (see below), prior to processing usingdistillation/evaporation. The isolated NR fraction is not typicallysubject to solvent or other fractionation processes used in the priorart, nor is it condensed (i.e. subject to condensation reactions) aswould be typically done for conventional, or vacuum pyrolysis liquidproducts. Without wishing to be bound by theory, it is possible that theomission of such condensation reactions during the production of the NRof this invention is a primary reason for the high reactivity of NR as aresin agent. However, it is to be understood that the production of NR,described herein, may include one or more solvent extraction, or otherconcentration or purification steps as required.

By “MNRP” it is meant an NR that has had the acids, water and othernon-reactive components removed via distillation/evaporation, or another analogous process, to produce a solid NR product. MNRP may beground, comminuted, and sized to a desired specification prior to use.

The NR of the present invention may be in the form of a liquid product,comprising activated lignin and spanning a range of viscosities fromabout 6 to about 130 cSt (@70° C.), for example, but not limited to NR60(e.g.NR60D-1H, NR60D-2H, NR60D-WH), and NR80 (e.g. NR80D-1H, NR80D-2H,NR80D-WH), or it may be a solid NR lignin product, for example, but notlimited to MNRP (e.g.MNRP-1H(70), MNRP-2H(70), MNRP-WH(70)) or“V-additive lignin”. Various viscosities of NR may also be produceddepending upon the temperature, duration and type ofdistillation/evaporation process used to produce NR. Liquid NR ischaracterized as being more polymerized, having a higher viscosity and ahigher average molecular weight than the oil feedstock. Examples ofschematics outlining the preparation of several NR's of the presentinvention are provided in FIGS. 2-5. With reference to these figures, itcan readily be seen that various combinations and permutations forprocessing the various oil feedstocks and NR's produced from thesefeedstocks, may take place. Therefore, it is to be understood that themethods outlined in these figures are examples of several methods forproducing NR, and are not to be considered limiting in any manner, asother NR's may be obtained by methods not disclosed within thesefigures.

NR is typically characterized by comprising a water content from about 2to about 20%, pH of about 2.0 to about 5.0, and acids content from about0.1 to about 5 (dry wt %) and a viscosity of about 6 to about 130 cST(@70° C.) for liquid NR, as in the case for example, but not limited toNR-60D, or the NR may be a solid NR as in the case of MNRP. Furthermore,NR is characterized as having an increased concentration of phenolicsand enhancers, as indicated by its NRP Index from about 50 to about 100,over that of light pitch (whole-oil), having an NRP Index of about 23 toabout 30 (see Tables 3a and 3b, Example 2). NR is also characterized ashaving a higher average molecular weight (AMW), when compared tolight-pitch. For example, NR-60D-WH has a wet AMW of about 306, and adry AMW of about 363, while light-pitch is characterized as having a wetAMV of about 232 and a dry AMW of about 299. MNRP has an even higher AMVof about 388 (wet) and about 412 (dry). The total phenolic content ofNR, for example, but not limited to NR60D-2H is from about 40 to about45% wt, and greater than that of whole-oil, from about 30% wt to about35% wt (See Table 3c, Example 2). The total phenolic content of MNRP isgreater than that of NR60D-2H.

A highly polymerized NR, called V-additive lignin is furthercharacterized as having a high phenolic content of about 95%, a watercontent of about 3%, and a melting point from about 110° C. to about150° C. (see Table 3d Example 2). This NR is a thermoplastic product andis suitable for use within industrial applications, for example as aplasticizer that can be used within foundry resin formulations as abinder for cores or admixed with moulding sand or clays, as an asphaltemulsifier, or as a concrete additive to increase the aeration qualityof concrete.

NR is more reactive, and comprises less acid and other odorouscomponents than the oil feedstock. The removal of acids ensures themaintenance of optimal resin properties upon rehydration, if required,and during the use of NR as an adhesive. Furthermore, a lower content ofacids requires less addition of caustic during adhesive formulationwhich otherwise weakens the wet property of the adhesive. V-additivelignin also has properties that make it suitable for a range ofdifferent industrial applications for example as a foundry resin,concrete additive, or asphalt emulsifier. NR obtained followingdistillation/evaporation comprises a complex mixture of enhancercompounds, for example, but not limited to, aldehydes and ketones, andactive phenolic compounds comprised of monomers and oligomers. NRtherefore has the ability to co-react with, or be used as a substitutefor, phenol within phenol/formaldehyde (PF) resins.

By “phenolics” or “ligninic” it is meant phenolic polymers which retainthe essential characteristics of their natural precursors (naturallignin is a phenolic polymer which holds wood and bark fibres togetherand which gives wood its strength), but are activated for use in resinformulations, or as additives in other industrial applications.

By “enhancers” it is meant carbonyl compounds, typically light aldehydesand ketones.

The NR-containing resins of the present invention may be used in thesame manner as phenol-formaldehyde resins are typically used. Forexample, which is not to be considered limiting in any manner, resinscompositions comprising NR may be used to produce industrial phenolformaldehyde resin products including mouldings, linings, insulation,foundry materials, brake linings, grit binders, for example, those usedwith abrasives such as sand paper, and the like. Furthermore, NRcomprising resins may be used as adhesives for the product of woodproducts and the like.

Fast pyrolysis of wood or other biomass residues results in thepreparation of product vapours and char. After removal of the charcomponents from the product stream, the product vapours are condensed toobtain a whole-oil, or bio-oil product from pyrolysis. A suitable fastpyrolysis process for preparing such a bio-oil is described in WO91/11499 (Freel and Graham, published Aug. 8, 1991, which isincorporated by reference), and is diagrammatically presented in FIG. 1.Briefly, the system includes a feed system (10), a reactor (20), aparticulate inorganic heat carrier reheating system (30), and for thepurposes of the invention described herein, at least one recovery unit,which as shown in FIG. 1, and which is not to be considered limiting inany manner, may comprise a primary (40) and a secondary (50) condenserthrough which the product vapours produced during pyrolysis are cooledand collected using a suitable condenser means (80). The recovery unitmay also include, a de-mister (60) and a fiber filter bed (70) or otherdevice to collect the liquid product. The NR of this invention may bederived from a selected product fraction obtained from at least onerecovery unit, for example the primary, or the secondary recovery unit,or a combination thereof, or it may be a whole-oil, obtained from firstand second recovery units, including de-misters and fiber filter bed, ora combination thereof. However, it is to be understood that analogousfast pyrolysis systems, comprising different number or size of recoveryunits, or different condensing means may be used for the selectivepreparation of the oil feedstock for the purpose of the presentinvention.

The recovery unit system used within the fast pyrolysis reactor system,outlined in FIG. 1, which is not to be considered limiting in anymanner, involves the use of direct-liquid contact condensers (80) tocool the pyrolytic oil product. However, it is to be understood that anysuitable recovery unit may be used. In the preferred embodiment, liquid,used within these condensers (80) to cool the pyrolytic product, isobtained from the corresponding cooled primary or secondary condenserproduct (90; FIG. 1). However, as would be evident to one of skill inthe art, any other compatible liquid for cooling the product within theprimary and secondary recovery units, or a combination thereof, may alsobe used for this purpose. Furthermore, it is considered within the scopeof this invention that other scrubber or cooling means including heatexchanges comprising solid surfaces and the like may also be used forcooling the product vapours. Bio-oils of the prior art may be processedusing. the methods of the present invention to produce a NR suitable foruse within adhesive formulations.

Suitable oil feedstocks for the purposes of the present invention may beproduced using the method and apparatus disclosed in WO 91/11499 (whichis incorporated by reference). These oil feedstocks are typicallycharacterized by the properties outlined in Example 1, however, it is tobe understood that the properties defined in Example 1 vary dependingupon the lignocellulosic feedstock used for fast pyrolysis. Other oilfeedstocks, comprising different properties than those listed in Example1 may be used for the methods as described herein.

An example, which is not to be considered limiting in any manner, ofconditions of distillation/evaporation for producing a liquid NRobtained from whole-oil, a selected product fraction, or a combinationthereof, comprises processing the oil feedstock at about 60° C. to about200° for about 1 to about 3 hours via roto-evaporation Preferably, theoil feedstock is maintained at about 110° C. to about 130° C. for about1 to about 1.5 hours during this processing step. Similar temperatureranges may be used to prepare a liquid NR using W.F.E., however, theduration of time where the oil feedstock is present within the W.F.E.apparatus is much shorter (i.e. the transport time through theapparatus), and the oil feedstock can be processed in a continuous andrapid manner. Typically following the distillation/evaporation step, andwhile the NR is still at about 60° C. to about 110° C., water may beadded to the NR to reduce the viscosity to the desired specification.The final liquid NR product so produced is characterized with aviscosity ranging from about 6.0 to about 130 (cSt @ 70° C.), andcomprises a water content level of from about 10 to about 25 wt %,preferably, the water content is from about 15 to about 18%. One exampleof a liquid NR produced using roto-evaporation, is NR60D-2H, which whensubjected to roto-evaporation for 1 hour at 120° C. and rehydrated, ischaracterized as having a viscosity of about 70 cSt.(@ 70° C.), a pH ofabout 2.6 and a low acid content of about 2.4 (Dry wt %). However, it isto be understood that by varying the oil feedstock anddistillation/evaporation processing parameters a variety of liquid NR'smay be produced.

An example, which is not to be considered limiting in any manner, ofconditions of distillation/evaporation for producing an MNRP (solid NR)obtained from whole-oil, a selected product fraction, or a combinationthereof, comprises processing the oil feedstock to roto-evaporation atabout 125° C. to about 220° C. for about 1 to about 3 hours. Preferably,the oil feedstock is maintained at about 160° C. to about 200° C. forabout 1 to about 1.5 hours. Temperature ranges of from about 90° C. toabout 160° C. may be used with W.F.E in order to process oil feedstockin a batch or continuous manner. An example of a solid NR produced inthis manner, is MNRP-1H(70), which may be produced by roto-evaporationfor 1 hour at 180° C. Typically, after cooling, the MNRP is ground andsized to produce a powder as a final product. A variety of solid NRproducts may be prepared by varying the feedstock, and processingparameters, including V-additive lignin.

The viscosity and degree of polymerization of liquid NR may also bevaried by pretreating a selected product fraction, prior to the step ofdistillation/evaporation. For example, which is not to be consideredlimiting, an NR with increased viscosity and degree of polymerizationover that of the oil feedstock may be obtained by subjecting a selectedproduct fraction obtained from the first recovery unit to a water wash,prior to distillation/evaporation, or prior to mixing it with a selectedproduct fraction obtained from the second recovery unit and thenproceeding with the step of distillation/evaporation as outlined above.Typically, water at about 30° C. to about 80° C., preferably from about40° C. to about 60° C., is added to the oil and mixed together, and theligninic NR liquid is allowed to concentrate. The non-ligninic liquidcomprises acids and other water-soluble components that reduce thereactivity of the final liquid or solid NR product. Separation andrecovery of the non-ligninic liquid concentrates the ligninic oilproduct. Furthermore, the addition of water to the oil feedstock priorto distillation/evaporation helps in the transfer of the oil feedstockduring processing. Water addition also helps to prevent the overcookingof the oil during distillati on/evaporation, and it may help enhance theremoval of non-resin components from the oil duringdistillation/evaporation by providing a carrier for such components. Anexample, which is not to be considered limiting in any manner, of awashed oil feedstock that is then processed by distillation/evaporationis NR80D-2H.

Therefore the final characteristics of NR may span a range ofviscosities and degrees of polymerization as determined by:

-   -   varying the temperature and treatment time during        distillation/evaporation;    -   the type of lignocellulosic feedstock used to produce the oil        feedstock, for example but not limited to oil feedstock produced        by fast pyrolysis;    -   the oil feedstock itself, whether it is a whole-oil, or a        selected product fraction, or a combination thereof;    -   the pretreatment of the oil feedstock; and    -   the amount of water added back to liquid NR.

Therefore, the present invention provides for a range of NR's, with arange of properties, including the degree of cross-linking,polymerization, enhancers, and active phenolic compounds, that may beused as replacements of constituents within adhesive resins, such asphenol formaldehyde, urea formaldehyde, or related resins, or as anasphalt emulsifier, concrete additive, foundry binder, as defined above.

By “phenol-containing formaldehyde resin” it is meant resin compositionsthat comprises phenol as one of its ingredients. Such resins include butare not limited to phenol formaldehyde (PF), phenolic melamine ureaformaldehyde (PMUF), and phenol urea formaldehyde (PUF) resins.Similarly, by “urea-containing formaldehyde resins” it is meant adhesivecompositions comprising urea as one of its ingredients, for example, butnot limited to, urea formaldehyde (UF), phenol urea formaldehyde (PUF),phenol melamine urea formaldehyde (PMUF), and melamine urea formaldehyde(MUF) resins. Without wishing to be bound by theory, it is thought thatthe addition of NR (in either solid or liquid form) to urea-containingresins adds or complements the phenol content of these resins due to thehigh phenolic content of NR. Therefore, a UF resin that is partiallyreplaced with NR may be considered a PUF-like resin.

Without wishing to be bound by theory, it is thought that the processingof the oil-feedstock using distillation/evaporation removes compoundsthat interfere with the use of bio-oils, for example those found withinthe prior art, within adhesive resin formulations. Furthermore, thedistillation/evaporation process has been found to actually increase theligninic and enhancer properties within the final NR product, over thatfound within the oil feedstock. As a result NR is comprised of apredominantly phenolic fraction, containing aldehydes, which provide NRwith its desirable properties for use within adhesive formulations. Inpart this quality of NR is indicated by its NRP (Natural Resin Pure)Index. For example, whole oil has an NRP Index of about 29, NR-60D hasan NRP Index of about 60, and MNRP is characterized with an NRP Index ofabout 90.

The oil feedstock of this invention may also be pretreated to reduce theorganic acid content of the resin prior to distillation/evaporation. Anysuitable method may be employed for this process, for example, and notwishing to be limited to this method, the feedstock may be washed inwater by mixing the feedstock in water, allowing phase separation totake place, and recovering the oil fraction. For example, which is notto be considered limiting in any manner, the oil feedstock is washed inwater from about 30° C. to about 80° C. and left to precipitate.Preferably, the water temperature is from about 40° C. to about 60° C.The pretreated feedstock prepared in this manner, comprises the phenolicand aldehyde content of the feedstock, with a dramatically reducedorganic acid content when compared with the initial feedstock, and is amore concentrate form of feedstock, containing up to about 80% (w/w)phenolics. This pretreated feedstock may be used for the preparation ofNR or MNRP as described herein, for example, but not limited toNR80D-2H.

The NR, or MNRP produced by the method described herein have beensubstituted for some of the phenol content within PF resins, and suchformulations meet or exceed current PF resin industry specifications. NRhas been substituted from about 60% to about 100% of the phenol contentwithin PF resins. Resins so produced may comprise up to about 40% (w/w)of NR. Similarly, NR may also be used as replacement within PMUF and,PUF resins. Furthermore, the NR of this invention has successfullyreplaced up to about 60% (w/w) of the urea formaldehyde within UFresins, and has been effectively used within PMUF and MUF resins. MNRPresins with even higher melting point temperatures, for example above110° C. may also be prepared using the methods as described herein.These high melting point resins are referred to as V-additive ligninsand has use within the automotive industry, or as a foundry resin,asphalt emulsifier, or as a concrete additive (see Table 3d, Example 2).

As a result of processing the NR using distillation/evaporation, therecovery technique is more selective than solvent extraction-basedmethods. For example, the P/N fraction extracted using ethyl acetate(e.g. U.S. Pat. Nos. 4,942,269; 5,235,021), results in a fractioncomprising a compound that is soluble in this solvent and that isco-extracted along with the desired-for resin compounds. Several ofthese co-extracted compounds are odorous (e.g. lactone, an acridcompound) while others dilute the P/N resin. Thedistillation/evaporation technique of this invention is selective inthat essentially all of the desirable resin components (naturalphenolics derived from lignin) are recovered, while other non-desiredcompounds are removed within other fractions. Furthermore, the processof distillation/evaporation has been found to increase the phenolic andenhancer components within NR, when compared to the oil feedstock. As aresult, the NR of this invention exhibits many beneficial propertiesover prior art pyrolytic oil extractions and requires significantly lesspreparation. For example:

-   -   1. NR and MNRP have a slight pleasant “smoky” odour, lacking the        acrid smell of solvent extracted fractions. When used within        adhesive applications and industrial resin applications, there        is no residual odour,    -   2. in solvent extracted processes, including the process used to        obtain P/N, the solvent reacts with residuals in the fraction        that is not used for P/N, to form salts. These salts must be        recovered using a recovery boiler requiring additional costs,        and the residual bio-oil is not available for other commercial        applications. NR or MNRP products, on the other hand, are not        contaminated with salts as no solvents are used;    -   3. the processing of oil feedstock by distillation/evaporation        is readily accomplished using simple devices and does not        require any specialized facilities for handling solvents and the        like;    -   4. the fast pyrolysis method used for the preparation of        bio-oil, including NR, has been successfully scaled up from        bench-top trials to industrial/commercial production levels (see        WO91/11499). Therefore, NR preparations are easily produced on a        commercial scale.        Characteristics of NR

The NR produced by the method of this invention has been found to beconsistent between batch to batch productions runs of NR (as tested whenused for OSB production, see below), even when different hardwoods andsoftwoods are processed by fast pyrolysis.

The free phenol content of a resin formulations is also used todetermine the suitability of alternative materials in PF resinformulations. The NR produced following the method of this invention ischaracterised in having a very low free phenol content, from about 0.001to about 0.05% (w/w), yet the total phenolic content is quite high, fromabout 30% to about 80% (w/w) within NR. It is the phenolic content whichis very reactive and provides an array of active sites for binding andcross linking within NR formulations.

NR refers to a range of products that are prepared according to themethods of the present invention. Several examples of such productsinclude, but are not limited to:

-   -   NR60D-WH    -   NR60D-1H    -   NR60D-2H    -   NR80D-2H    -   MNRP-1H(70)    -   MNRP-2H(70)    -   V-additive lignin.        Also see FIGS. 2-5

The above nomenclature is to be interpreted as follows: NR60D-WH, is aliquid NR with an Natural Resin Pure Index (NRP) of 60. The NRP index isa measure of the phenolic and enhancer content of the NR. A higher NRPindex indicates a greater proportion of phenolics and enhancers. The “D”associated with NR60, indicates that the NR has been processed bydistillation/evaporation (MNRP due to its nature has been processedusing distillation/evaporation, and therefore lacks the “D”designation). The oil feedstock for the preparation of the NR may be awhole-oil obtained from a range of lignocellulosic feedstocks, forexample hardwood, and “WH” designates such a oil feedstock. The 1H or 2Hdesignation indicates that the oil feedstock is obtained from theprimary or secondary recovery unit, respectively, using a hardwoodlignocellulosic feedstock (other lignocellulosic feedstocks may also beused). MNRP indicates that the NR is solid. The 1H or 2H designation isthe same as above, while “(70)” indicates that the melting point of theM is 70° C. V-additive lignin is a highly polymerized MNRP characterizedin that it has a melting point above 110° C.

Several of these NR's are characterized by the parameters listed inExample 2 however, it is to be understood that other NR may be producedwith properties that differ from those listed in Example 2.

The final NR product of this invention comprises up to about 20% water,however, NR is insoluble in water due to its low polarity and highcontent of non-polar organics. By increasing the pH of the NR (to about10) and converting it into its phenoxide ion form it obtains a gum-likeconsistency, is water soluble and can be used within formaldehyde-phenolformulations. MNRP is not soluble in water and is used in its powderedform within adhesive formulations. NR, both solid and liquid, is solublein polar organic solvents for example acetone, methanol, ethanol andisopropanol. Due to the hydrophobicity of NR, it is chemicallycompatible in the formulation of phenolic-based resins. Liquid NR issoluble in a mixture of water/phenol, and when reacted withformaldehyde, gives methyol-water soluble derivatives. Liquid NR (forexample NR60) and solid NR (for example MNRP) are both soluble in thebasic formulation of a P/F

When compared with whole-oil, NR is typically characterized bycomprising a lower water and acid content, a higher viscosity, NRP Indexand average molecular weight than whole oil. For example, which is notto be considered limiting in any manner, a comparison of NR60D-2H withwhole-oil indicates that NR60D-2H comprises:

-   -   a lower water content (from about 5 to about 20 wt %), than that        of whole-oil (about 23-30 wt %);    -   a lower acid content of about 0.1 to about 5 dry wt %, compared        with an acid content of about 7 to about 12 dry wt % of whole        oil;    -   a viscosity of about 20 to about 130 cST (@70° C.), compared        with a viscosity of whole oil of about 5 to about 10 cST (@70°        C.);    -   an increased concentration of phenolics and enhancers (NRP Index        from about 50 to about 100), compared with whole-oil having an        NRP Index of about 23 to about 30;    -   a higher average molecular weight (wet—about 306; dry about 363)        compared to whole oil (wet—about 232; dry about 299); and    -   a total phenolic content from about 40 wt % to about 45 wt %,        compared with that of whole-oil, from about 30 wt % to about 35        wt %.

A higly polymerized NR with a high melting point typically about 110° C.is called V-additive lignin. This NR is produced by increasing the time,temperature, or both time and temperature duringdistillation/evaporation. V-additive lignin is characterized as having ahigh phenlic contect of about 95%, a water content of about 3%, amelting point from about 110° C. to about 150° C., a flash point greaterthan 280° C., and a density of about 25C g/cm(see Table 3d Example 2).V-additive lignin may be commuted to a powder or produced in aflake-like form prior to use. This NR is a thermoplastic product and issuitable for use within industrial applications, for example as aplasticizer that can be used within foundry resin formulations andadmixed with sand, as an asphalt emulsifier, or as a concrete additiveto increase the aeration quality of concrete. V-additive lignin may alsobe used within the automotive industry.

Calometric analysis indicates that NR has a net caloric value of about4355 cal/g (18.22 MJ/kg), with a gros caloric value of about 4690 cal/g(19.62 MJ/kg).

NR may be obtained from a variety of lignocellulosic feedstock sourcesincluding softwood, hardwood, bark, white wood, or other lignocellulosicbiomass feedstocks, for example, bagasse (sugar cane residue).

NR-containing Phenol Formaldehyde (PF), or Urea Formaldehyde (UF) Resins

In order to formulate NR within phenol-containing formaldehyde, orurea-containing formaldehyde resins, phenol or urea, water,paraformaldehyde, and other ingredients of the adhesive are mixedtogether and heated if required to dissolve the ingredients. If heated,the mixture is cooled prior to the addition of NR. Caustic (for exampleNaOH) is added to the mixture containing phenol or urea, formaldehydeand NR, to a desired pH. The addition of caustic ensures thesolubilization of the NR, and initiates the reaction. This mixture maythen be heated or cooled, and more caustic added during the preparationof the resin, as required. The resin is typically maintained at 10° C.until use, and exhibits similar stability associated with commercial PFresin formulations. Phenolic melamine urea formaldehyde (PMUF), melamineurea formaldehyde (MUF), phenol urea formaldehyde (PUF) resins areprepared in a similar manner.

NR can be added up to about 60% to about 100% (w/w) of the phenolcontent of the resin. Furthermore, the formaldehyde content ofphenol-containing or urea-containing resins may be substituted with NRdue to the natural aldehydes present within NR, for example NR can beused to replace up to about 50% (w/w) of the formaldehyde content ofthese resins. Similarly, up to about 60% (w/w) of the urea-formaldehydecontent of a UF resin may be replaced using NR. Therefore, PF, UF andrelated resins may be formulated that contain up to about 40% (w/w) NRof the total resin composition. As disclosed in Example 3, NR producedas described herein is suitable for use as a phenol substitute within PFresins. However, this is not the case for Whole-oil (light pitch), whichwhen used within PF resins as a substitute for 40% phenol, producedinferior OSB and waferboard panels (see Example 3, Table 5) that did notmeet CSA Standard 0437.093.

Resins prepared using NR may be used for a variety of purposesincluding, but not limited to, the preparation of wood products, forexample, laminated wood, plywood, particle board, high density particleboard, oriented strand board, medium density fibre board, hardboard, orwafer board. Furthermore, NR-containing resins may also be used for themanufacture of industrial phenol formaldehyde resin products, forexample, but not limited to, mouldings, linings, insulation, as foundryresins, asphalt emulsifiers, concrete additives, for brake linings, asgrit binders and the like.

Board Manufacture Using NR-containing Resins

The phenol-containing or urea-containing formaldehyde resins preparedabove may be used for the production of a range of board products, forexample, but not limited to, laminate wood boards, plywood, particleboard, high density particle board, oriented strand board, mediumdensity fiber board, hardboard, or wafer board. NR-containing PF resinsare used within boards to be subject to exterior use due to theexcellent water repellency of the resin. Typically UF resins are notdesired for outside use, however, NR-containing UF resins may haveapplication for exterior use due to the reduced swelling observed inboards prepared with urea formaldehyde adhesives comprising NR, comparedwith boards prepared using commercial UF resin.

NR containing PF or UF resins can be used for the production of orientedstrand board (OSB) as outlined below. However, it is to be understoodthat this application of NR-containing resin is not to be consideredlimiting in any manner, as other wood derived products prepared usingcommercially available PF, UF, or related resins, which are commonlyknown within the art, may be prepared using resin formulationscomprising NR.

Oriented strand boards may prepared using standards methods that areknown to those of skill in the art. For example, but not to beconsidered limiting in any manner, the production of OSB may involve thefollowing parameters:

-   wood matrix: particulate wood product, wood chips, wafers, veneer or    plywood etc.-   Panel thickness: from about {fraction (1/16)}″ to 2″-   Resin content: from about 0.5 to about 20.0%-   Wax content: from about 0.5 to about 5%-   Mat moisture: from about 2 to about 10%-   Press time: from about 2 min to 30 min-   Press temperature: from about 150° C. to about 275° C.    It is to be understood that these parameters may be adjusted as    required in order to produce a suitable board product using    NR-containing resins of this invention.

Oriented strand boards, or other board types, as listed above, that areprepared using NR-containing PF resins are readily tested forsuitability within the industry. For example, the OSB boards prepared asdescribed herein have been tested according to the Canadian productstandard for OSB (CSA 0437.1-93, April 1993). These tests include;determination of density, internal bond (IB), modulus of rupture (MOR),and modulus of elasticity (MOE) and the minimum properties to meet thisstandard are listed below (Table 1):

TABLE 1 CSA 0437.103 Standard Parameter Grade R-1 Units Modulus ofRupture (MOR) 17.2 MPa Modulus of Elasticity (MOE) 3100 MPa MOR after2-h boil (wet) 8.6 MPa Internal Bond (IB) 0.345 MPa Thickness Swell 15 %Water Adsorption N/A %

Results of these tests indicate that phenol may be replaced by NR fromabout 10 up to 100% (w/w), and produce a OSB product that meetsindustrial standards, and that is equivalent to, or exceeds OSBsprepared using commercially available phenol-containing, orurea-containing formaldehyde resins. Furthermore, OSB boards preparedwith NR-containing resins require less formaldehyde within resinformulations for equivalent cross-linking and binding properties astypically found with control resin formulations.

Without wishing to be bound by theory, it is thought that the naturalcarbonyl components (such as aldehydes and ketones) within NR permitsthe use of less formaldehyde. In applications which require lowerstrength adhesive, the NR can be used alone without any addition offormaldehyde, but it is preferable to add formaldehyde to obtain abetter resin. These carbonyl compounds have a molecular weight fromabout 30 to about 800 Daltons, and comprise about 23% of the NR

The NR produced following the method of this invention has a dark browncolour, and when formulated into a resin, results in a dark reddishbrown colour. However, during production runs using NR, OSB boards arelighter in colour than PF control boards. Furthermore, the NR has amild, pleasant odour, yet OSB boards prepared using NR have no resultantodour. The odour can be reduced following heating of the NR, or throughthe removal of volatiles via flushing. The NR of this invention is alsocharacterized by being acidic (pH ˜2.3), however, the acid content of NRis substantially reduced compared with that of the oil feedstock.

The above description is not intended to limit the claimed invention inany manner, furthermore, the discussed combination of features might notbe absolutely necessary for the inventive solution.

The present invention will be further illustrated in the followingexamples. However it is to be understood that these examples are forillustrative purposes only, and should not be used to limit the scope ofthe present invention in any manner.

EXAMPLES Example 1

Method for Obtaining, and the Characteristics of, Oil Feedstocks

Oil feedstock is obtained using red maple feedstock within a fastpyrolysis reactor as described in WO 91/11499 (which is incorporatedherein by reference). Red maple feedstock is supplied to the reactor ata feedstock to heat carrier ratio of from about 5:1 to about 200:1. Thechar is rapidly separated from the product vapour/gas stream, and theproduct vapour rapidly quenched within the primary recovery unit using,for example, a direct liquid contact condenser. The compounds remainingwithin the product vapour are transferred to a secondary recovery unitlinked to the primary recovery unit in series. The product vapour isthen quenched using, for example a direct-liquid contact condenserwithin the secondary recovery unit, and the condensed product collected.Any remaining product within the product vapour is collected within thedemister and filter bed (see FIG. 1). The primary recovery unit productis collected, as well as the secondary recovery unit product. The yieldof product oil, using red maple as a feedstock, from the primaryrecovery unit ranges from about 40 to about 60% (w/w), and is typicallyabout 53.3%. The yield of oil from the secondary recovery unit rangesfrom about 12 to about 25% (w/w) and is typically about 19.7%.

The oil feedstock is characterized as exhibiting a low free phenolcontent ranging from 0.001 to 0.1% (w/w); total phenolic content fromabout 10-80% (w/w); a dark brown colour and a mild, pleasant smokyodour, a pH of about 2.0 to about 2.8 (see Table 2); insolubility inwater, and solubility in organic solvents including acetone, methanol,ethanol and isopropanol.

TABLE 2 Properties of Oil feedstock Water Acid Viscosity content Content(cSt @ NRP A.M.W.* Oil feedstock pH (wt %) (Dry wt %) 70° C. IndexWet/Dry Primary 2 36 12 3 22 n/d*** Recovery unit Secondary 2 18 8 15 48n/d Recovery unit Whole-oil** 2 24 10 6 30 232/299 *Average MolecularWeight **combination of primary and secondary recovery unitoil-products. ***not determined

The oil feedstock is optionally washed with 3 volumes water at 50° C.,the phases allowed to separate, and the oil-layer retained, to produce awashed oil feedstock that is characterized in having a more neutral pH,and up to 90% less organic acid content when compared with the oilfeedstock. Furthermore, the phenolic content of washed oil feedstock isup to about 80% (w/w) or more, due to the removal of the organic acidcomponent, and is a more concentrate form of oil feedstock.

Example 2 Preparation and Analysis of Liquid NR, MNRP and V-additiveLignin

Liquid NR Production Using Rotoevaporation

Oil feedstocks from Example 1 are processed by distillation/evaporationat 120° C. for 1 hour under vacuum of 26″Hg to a water content of about3% (wt %) to produce an NR. The product is removed and water is added tothe liquid NR when the NR reaches a temperature of about 80° C. to makea final water content of 16-18 (wt %). The NR is mixed well and allowedto cool to room temperature.

Liquid NR is typically characterized by comprising a water content offrom about 10 to about 20 wt %, pH of about 2.0 to about 5.0, an acidscontent from about 0.1 to about 5 (dry wt %), an average molecularweight (wet)/(dry) of from about (250-350)/(280-380) Daltons, and aviscosity of about 6 to about 130 cST (@70° C.). Analysis of liquid NRis presented in Tables 2 and 3 below.

Solid MNRP Production Using Rotoevaporation

Oil feedstocks from Example 1 are processed by distillation/evaporationat 180° C. for 1 hour under vacuum of 26″Hg. The product is decantedwhile hot, cooled to solidify, and ground to a powder. To produce anMNRP with an 80° C. or a 100° C. melting point, the oil feedstock isrotoevaporated for 1 hour 10 min, or 1 hour 20 min, respectively.

Solid NR is characterized by comprising a water content of from about 3to about 10 wt %, pH of about 2.0 to about 5.0, an acids content fromabout 0.1 to about 5 (dry wt %), an average molecular weight (wet)/(dry)of from about (300-450)/(350-500) Daltons, and is a solid at roomtemperature.

Examples of the properties of several solid NR's prepared from primary,secondary recovery units are presented in Table 3. These parameters aretypical for each defined sample, however, they are obtained from onesample and variations in these values are to be expected.

Both the liquid and solid NR's are generally characterized as having alower acid content, higher pH, higher viscosity, an increased averagemolecular weight, and a higher concentration of phenolics and enhancersas indicated by the NRP Index, than the oil feedstock (compare Tables 2,above and Table 3, below).

Wiped Film Evaporation of NR

Oil feedstocks from Example 1 are processed by WFE at 80° C., for liquidNR, or 140° C. for MNRP, in a continuous or batch mode under vacuum of26″Hg. The oil feedstock is added to the WFE at a feed rate within arange of 20 to 50 lbs./hr per square foot of heated surface area. Onceliquid is observed flowing through the viewing port on the resin outletof the WFE, the rotor is turned on between 130 and 300 revolutions perminute. The liquid is distributed centrifugally to the heated wall and afilm is created by the moving wiper blades. All pipes used to transportthe NR are heated to 150° C. The concentrated resin is tapped off afteran appropriate amount of time.

Batch System

Vacuum is isolated with top valve of resin vessel and resin is drainedinto a container. When all resin has drained, the drain valve is closedand the vacuum is reintroduced to vessel. The concentrated resin isweighed, and for liquid NR, an appropriate amount of water to produce aproduct with 16% to 18% by weight is added. The product is mixedthoroughly with drill mixer and a sample is taken for analysis. No wateris added for MNRP (solid NR).

Continuous System

A height for the level setpoint is set and the bleed line control valveis adjusted to the mixing tank to keep this level constant. For liquidNR, the water flow rate setpoint is set to a value that produces aproduct with a water content of 16% to 18%. A high shear mixer mountedon mixing vessel is used to mix water and resin thoroughly. Periodicallytake samples for analysis. No water is added for MNRP.

NR's produced from primary or secondary recovery units, or whole oil,using WFE exhibit the same properties as those listed in Table 3, below.

Yields of NR60D-1H, using red maple as the lignocellulosic feedstock,ranges from about 16 to about 26% (w/w), and typically are about 23%(w/w). Yields of NR60D-2H range from about 12 to about 20% (w/w), andare typically about 17% (w/w). Yields of HR60D-WH range from 32 to about48% (w/w) and are typically 40% (w/w).

Examples of the properties of several NR's prepared from the secondaryrecovery unit or whole-oil fraction are presented in Tables 3a and 3b.These parameters are typical for each defined sample, however, they areobtained from one sample and variations in these values are to beexpected.

TABLE 3a Properties of NR Water Acid content A.M.W.* NRP MeltingViscosity @ NR content (wt %) pH (Dry wt %) Wet/Dry Index Point (° C.)70° C. (cSt) NR60D-WH 16.5 2.6 2.4 306/363 60 liquid 110 NR60D-2H 16.52.6 2.4 287/340 60 liquid  70 MNRP-1H(70) 6 2.5 0.7 n/d** 90 70 solidMNRP-2H(70) 6 2.5 0.7 388/412 90 70 solid *Average Molecular Weight,Daltons **not determined

TABLE 3b Detailed properties of NR-60D-2H compared with Whole OilCharacteristic Whole Oil NR-60D-2H pH 2.26 2.36 Water Content (wt %)23.4 17.4 Acid Content (dry wt %) 9.9 2.4 Viscosity @ 70° C. (cSt) 8 70NRP Index 29 61 Ash Content (wt %) 0.08 0.03 AMW (wet/dry) 232/299287/340 Carbon 44.90 51.22 Hydrogen 7.33 6.89 Nitrogen 0.21 0.29 Sulfur0.05 0.05 Oxygen 24.03 24.12A comparison of the phenolics, as determined by GC(TOF)MS within ofwhole-oil and NR60D-2H is provided in Table 3c. The data in this Tableare an extract of the analysis, highlighting most of the phenolics inthese samples, and indicate that the total phenolic content (determinedfrom the complete analysis) of whole-oil is about 33.9 wt %, and forNR60D-2H, the total phenolic content is about 42.5 wt %.Table 3c

Comparison of phenolic content between whole-oil and NR60D-2H derivedfrom GC(TOF)MS analysis (* R.T. Retention Time in secs. These areapprox. times using whole oil analysis for the reference R.T. Variationsin time exist between analysis. Where times differ between whole oil andNR60D-2H. the R.T. is left blank).

Whole Oil NR60-2H R.T.* Name Area % Peak # Area % Peak # 241.61 Phenol6.5061 41 4.3904 40 364.11 Phenol, 2-methyl 1.7123 66 1.5168 69 412.11Phenol, 2-methoxy 2.0703 74 2.2143 79 452.61 Phenol, 2,3-dimethyl0.32788 82 0.30263 89 543.11 Phenol, 2-ethyl 0.40623 93 .084498 108558.12 Ethanone, 1-(2-hydroxyphenol) 0.024522 111 560.61 Phenol,2,4-dimethyl 0.25740 95 .64672 112 564.11 Phenol, 2-(2-propenyl)-(Tent)0.024792 96 DB5-802 567.61 2,5-Dihydroxybenzaldehyde 0.074999 97 .27138114 608.11 Phenol, 4-ethyl 0.042256 101 614.11 Phenol, 2-ethyl 0.033676104 627.61 Phenol, 3-4-dimethyl 0.17496 105 644.61 Phenol,2-methoxy-4-methyl 1.2882 108 .36706 119 Phenol, 3-ethyl 0.037461 120665.61 Phenol, 3,4-dimethyl 0.13768 112 .15799 121 Phenol,2-methoxy-4-methyl 1.4152 123 666.12 Phenol, 3,4-dimethyl 0.15818 128672.11 Phenol, 2,4,6-trimethyl 0.21058 113 .15089 129 700.611,2-Benzenediol 0.74677 117 .017686 134 748.12 Resorcinol Monoacetate0.26544 138 752.61 Phenol, 3-(1-methylethyl)- 0.19326 120 .16743 139773.61 Phenol, 3-(1-methylethyl) 0.64036 122 0.64365 141 785.11 Phenol,3-(1-methylethyl) 0.078711 126 806.11 1,2-Benzenediol.3-methoxy 0.092985127 1.3222 144 809.11 Phenol, 4-ethyl-2-methoxy- 0.050523 128 0.58397146 819.11 Phenol, 2-(2-propenyl), (Tent) 0.021504 129 DB5-802 836.62Phenyl, 3,4,5-trimethyl 0.052516 149 836.61 1,2-Benzenediol, 4-methyl0.0044058 134 0.93860 150 853.11 Phenol, 4-ethyl-2-methoxy 0.10123 138.11244 152 889.12 Thymol 0.18315 157 889.11 Phenol, p-tert-butyl 0.15713142 914.61 1,2-Benzenediol,4-methyl 0.063533 146 923.11 Benzene,(3-methyl-2-butenyl)- 0.034630 147 935.11 4-Hydroxy-3- 0.24843 148methylacetophenone 949.11 Phenol,2-(1,1-dimethylethyl)-5- 0.0091629 151methyl- 956.61 Benzaldehyde,4-hydroxy 0.085893 152 1033.12-Methoxy-5-methylphenol 0.27300 158 917.62 1,2-Benzenediol, 4-methyl1.5103 160 960.12 Benzaldehyde, 4-hydroxy 0.37630 165 1034.1 Phenol,2-methoxy-4-methyl 0.31506 173 1034.6 Phenol, 2,6-dimethoxy 1.3823 1591.9856 174 1045.1 Phenol, 2-methoxy-5-(1- 0.20728 162 .28363 175propenyl)-,(E)- 1057.6 1,4-Benzenediol,2-methyl 0.068245 164 .032946 1781060.1 Phenol, 2-methoxy-4-propyl 0.25673 179 1092.6 Benzaldehyde,4-hydroxy 0.075885 167 1133.6 Vanillin 0.68202 173 .055973 182 1138.11,3-Benzenediol, 4-ethyl 0.25115 174 1140.1 1,3-Benzenediol, 4-ethyl0.35844 183 1163.1 Phenol, 2-methoxy-4-(1- 0.14949 177 0.19770 186propenyl)- 1169.1 Ethanone, 1-(2- 0.10464 187 hydroxyphenyl)- 1228.61,3-Benzenediol, 4-ethyl 0.071847 190 .037727 194 1245.6 4-Nonylphenol0.018417 194 1254.1 Benzoic acid, 4-hydroxy-3- 0.27811 196 methoxy1229.6 Benzeneacetic acid, α,4- 0.087292 197 dihydroxy 1255.1 Ethanone,1-(2,3,4- 0.21500 199 trihydroxyphenyl) 1257.1 Phenol, 2-methoxy-5-(1-0.29094 197 .37792 200 propenyl)-,(E)- 1272.6 Phenol, 4-ethyl-2-methoxy0.046344 200 .062325 202 1277.6 Ethanone, 1-(2-hydroxyphenyl) 0.12035203 1281.6 Benzaldehyde, 2-hydroxy-, 0.042618 204 oxime 1317.1Benzeneacetaldehyde, α-phenyl 0.012898 209 1333.13-tert-Butyl-4-hydroxyanisole 1.1684 210 1280.1 Benzoic acid,4-methyl-,2- 0.035040 201 methylpropyl ester 1282.6 Phenol,2-methoxy-4-propyl 0.12796 202 1344.6 Eugenol 0.019586 210 1351.1Levodopa 0.034104 211 0.49220 212 1386.1 Phenol, 4-ethyl-2-methoxy0.040772 215 1397.1 1-Naphthalenol 0.063726 216 1403.6 Phenol,2,4-bis(1,1- 0.054585 217 dimethylethyl)- 1424.6 ButylatedHydroxytoluene 12.087 218 10.861 219 1426.6 Phenol,4-(2-aminopropyl)-,({overscore (n)}) 0.070690 220 1434.6 Phenol, 4-[2-0.042206 219 .047516 221 (methylamino)ethyl] 1472.6 Phenol,2-methoxy-5-(1- 0.10844 224 propenyl),-(E) 1519.63-tert-Butyl-4-hydroxyanisole 0.031443 225 0.031278 227 1520.13-tert-Butyl-4-hydroxyanisole 0.031278 227 1536.1 Phenol, 2,6-bis(1,1-0.044237 229 dimethylethyl)-4-ethyl- 1538.1 Phenol, 4-ethyl-2-methoxy0.049476 230 1553.6 3-tert-Butyl-4-hydroxyanisole 0.10967 234 1566.1Ethanone, 1-(2,3,4- 0.070903 238 trihydroxyphenyl) 1570.6 Ethanone,1-4-hydroxy-3- 0.055395 237 .092669 240 methoxyphenyl)- 1577.6Benzaldehyde, 2,4-dihydroxy- 0.027003 238 .0083349 241 3,6-dimethyl1617.1 Phenol, 2,6-dimethoxy-4-(2- 0.19601 244 .30014 246 propenyl)-1647.6 Benzeneacetic acid, 3,4- 0.14553 249 dihydroxy- Benzeneaceticacid, 4-hydroxy- 0.18419 250 3-methoxy Phenol, 2,6-dimethoxy-4-(2-.19360 251 propenyl) 1686.1 Phenol, 4-methyl-2-nitro 0.13512 252 1706.1Benzeneacetic acid, 4-hydroxy- 0.10507 254 3-methoxy- 1718.1 Phenol,2,6-dimethoxy-4-(2- 0.14338 255 propenyl) 1732.6 Benzaldehyde,4-hydroxy-3,5- 1.2295 256 2.3095 252 dimethoxy 1774.6 Benzoic acid,2,4-dihydroxy- 0.027131 256 3,6-dimethyl-, methyl ester 1820.6 Phenol,2,6-dimethoxy-4-(2- 0.39642 262 .32717 260 propenyl)- 1862.1Benzeneacetic acid, 4-hydroxy- 0.084137 263 3-methoxy-, methyl ester1872.1 Phenol, 2,4,6-tris(1,1- 0.056578 270 dimethylethyl) 1931.13,5-di-tert-Butyl-4- 0.14329 277 .15838 269 hydroxybenzaldehyde 1944.1Benzaldehyde, 3-hydroxy-4- 0.020640 270 methoxy 2006.1 Benzeneaceticacid, 3,4- 0.035096 281 dihydroxy 2058.1 Phenol, 2,6-dimethoxy-4-(2-0.010906 286 propenyl) 2069.1 Benzaldehyde, 4-hydroxy-3,5- 0.060959 289dimethoxy 2152.1 Phenol, 2,6-bis(1,1- 0.029731 291dimethylethyl)-4-ethyl 2211.6 Phenol, 2,6-bis(1,1- 0.029997 295dimethylethyl)-4-ethyl 2172.1 3,5-di-tert-Butyl-4- 0.059165 296hydroxybenzaldehyde 2301.1 Phenol, 2,6-bis(1,1- 0.042017 298 .051196 299dimethylethyl)-4-ethyl 2377.6 Phenol, 2-methyl-4-(1,1,3,3- 0.045775 302tetramethylbutyl) 2463.6 Benzaldehyde, 4-hydroxy-3,5- 0.027143 305dimethoxy 2473.1 Phenol, 2,6-bis(1,1- 0.051792 305dimethylethyl)-4-ethyl 3755.1 Benzaldehyde, 4-hydroxy-,(2,4- 0.018597313 dinitrophenyl)hydrazoneV-Additive Lignin

A NR with a high melting point, greater than about 110° C. is calledV-additive lignin, and may be made using any of the processes describedabove however, the time during distillation/evaporation process isincreased, and the temperature during distillation/evaporation is alsoincreased. Characteristics of V-additive lignin are presented in Table3d. V-additive lignin is a highly polymerized MNRP, it is commuted to apowder or produced in a flake-like form prior to use. V-additive ligninis a thermoplastic product and is suitable for use within industrialapplications, for example as a plasticizer that can be used withinfoundry resin formulations and admixed with sand, as an asphaltemulsifier, or as a concrete additive to increase the aeration qualityof concrete. V-additive lignin may also be used within the automotiveindustry.

TABLE 3d Anlaysis of V-Additive Lignin Properties V-Additive LigninMelting Point ° C. 110-150 Gasoline Soluble % 1 Ash % 0.01 FlashPoint >280 Density 25 C g/cm3 1.19 Hydroxyl % 1.4 Methoxyl Content % 5.3Colour Dark Brown Chemical Composition Phenolic Fraction 95 HydrocarbonFraction 0.1 Rosin-Derived Fraction (acids) 1 Water 3 Ester, Aldehyde,Alcohol 0.9

Example 3

Replacement of Phenol within NR-containing PF Resins and Their Use inOSB Manufacture

The NR produced according to the method of Example 2 is formulated intoa resin according to industry standards except that 40% of the phenolcontent is replaced by the NR. The adhesive resin comprised aformaldehyde:(phenol+NR) ratio of 1.6:1. An adhesive prepared from aBio-oil-WH (i.e. the whole-oil feedstock), that had not been processedby distillation/evaporation is included for comparison.

Typical NR resin formulations involved loading phenol, water andparaformaldehyde into a kettle and heating to 95° C. to dissolve theparaformaldehyde. The mixture is cooled to 45° C. and the NR added.Caustic (NaOH) is then added to the desired pH thereby solubilizing theNR and initiating the reaction. During the addition of caustic, themixture is maintained at 45° C. for the first caustic addition(approximately ⅔ of the amount required). The mixture is then slowlyheated to 90° C. over a 30 min period over which time the resin ismonitored for viscosity and subsequently cooled prior during which theremaining caustic is added. The resin is maintained at 10° C. until use.The resultant formulations are characterized in Table 4.

TABLE 4 Adhesive Characterization for OSB Solids Free Gel Amount NRportion of Viscosity content CHOH Time of Caustic resin (cps) (%)* (%)(sec) pH (wt %) NR60D-WH 78 41.7 1.21 <600 10.44 7.97 NR60D-2H 81 41.881.36 684 10.45 8.6 MNRP-1H(70) 120 44.06 1.56 521 10.67 9.57 MNRP-2H(70)101 43.78 2.11 672 10.46 8.09 Biooil-WH 70 40.37 0.8 733 10.53 7.97*determined by heating resin sample at 105° C. for 16 hours

The OSB's are prepared following standard industrial procedures usingone of the adhesive resins listed in Table 4 as well as a control(commercial) resin. The parameters for OSB production are as follows:

Strands: 3 inch poplar from an OSB mill Panel type: homogenous Panelthickness: 7/16″ Panel size: 18″ × 18″ Resin content: 2.0% (solidsbasis) Wax content: 1.5% Mat moisture: 5.5% Total Press time: 180 secPress temperature: 215° C. Press pressure: 1350 psi Replication: 4

The prepared OSB are tested for the following properties: density, IB(internal bond), MOR (modulus of rupture), and MOE (modulus ofelasticity), according to the Canadian product standard for OSB (CSA0437.1-93, April 1993). Twenty OSB panels are manufactured using thefive resins (4 NR-based resins and one control). The panels are testedright after pressing, without conditioning. The test results arepresented in Table 5

TABLE 5 Summary of OSB Panel Test Results NR-based Density of IB MOR(MPa) MOE Torsion Shear Thickness Water resin IB sample (MPa) Dry Wet(MPa) Wet (in.lb) Swelling (%) Absorption (%) Control 670 0.586 34 15.74300 40.9 15.4 30 NR60D-WH 670 0.46 37.2 17.6 4600 26.1 18.7 33.6NR60D-2H 669 0.553 36.3 15.7 4700 36.6 17.7 32.1 MNRP-1H70 671 0.593 3517.3 4700 34.1 17.9 33.2 MNRP-2H70 670 0.558 29.8 18.1 4000 40 16.3 32.6Biooil-WH 652 0.419 26 14.9 4100 20.5 18.9 40.1

Panels produced using a resin composition comprising NR, substituted for40% of phenol, exhibit properties equivalent to that of the commercialPF resin composition. The OSB prepared using NR based resins does notexhibit any difference in appearance compared with OSB's prepared usingPF resins. The NR-based resins exhibit better properties than theBiooil-WH (light pitch) based resin that had not been processed usingdistillation/evaporation. The Biooil-WH bonded panels did not meet OSBand wafer board specifications as set out in CSA Standard 0437.093.

The panels produced using NR-based resins exceeded the CSA Standard(0437.0-93) for all parameters, except for thickness swelling. As thepanels are tested right after pressing without conditioning, it isexpected that thickness swelling and water absorption could be loweredby conditioning the panels to a constant mass and moisture content priorto the test. Furthermore, as the NR-based resins have a lower viscosityand alkalinity, the adhesive easily penetrates into the veneer and maystarve the glue joint. Optimization of the penetrating property of theseresins will increase bonding strength and associated properties.

These results indicate that a substantial proportion of phenol within PFresin formulations may be replaced with NR and the resultant adhesiveperforms as well, or exceeds the performance of commercially availableresins. Furthermore, these results indicate that the processing ofwhole-oil (light pitch) as described herein produces an NR suitable forPF resin use.

Example 4

Replacement of Phenol within NR-containing PF Resins and Their Use inPlywood Manufacture

The NR produced according to the method of Example 2 is formulated intoa resin according to industry standards except that 40% of the phenolcontent is replaced by the NR. The adhesive resin comprised aformaldehyde:(phenol+NR) ratio of 1.6:1. NR-based resin formulationswere prepared as follows: water (125.4 g; 13.2 wt %) is mixed with sodaash (4.75 g; 0.5 wt %) for 5 min. To this wheat flour (63.7 g; 6.7 wt %)is added and mixed for 10 min. NR (337 g; 35.5 wt %), NaOH (50%solution, 26.6 g; 2.8 wt %) and Cocob (55.1 g; 5.8 wt %) are added andmixed for 15 min. A further amount of NR (337.5 g; 35.5 wt %) is addedand mixed for 15 min. Commercial plywood resin is also preparedaccording to industry standards. The resultant formulations arecharacterized in Table 6.

TABLE 6 Adhesive Characterization for Plywood Solids Free Gel Amount ofNR portion of Viscosity content CHOH Time Caustic resin (cps) (%)* (%)(sec) pH (wt %) NR60D-WH 1385 42.98 0.5 <500 10.44 7.97 NR60D-2H 112042.02 0.6 476 10.45 8.6 MNRP-1H(70) 1070 44.35 0.91 446 10.67 9.57MNRP-2H(70) 1125 44.28 1.48 558 10.46 8.09 *determined by heating resinsample at 105° C. for 16 hours

Plywood panels are prepared following standard industrial proceduresusing one of the adhesive resins listed in Table 5 as well as a control(commercial) resin. The parameters for plywood panel production were asfollows:

Panel construction: 3 ply, 305 × 305 mm (12″ × 12″), yellow birch Veneerthickness: 1.5 mm Veneer moisture: 8.6% Glue spread: 20 g/ft² (215 g/m²,or 44 lb/1000 ft²) Open assembly time: 5 min* Press time: 3,4,5,7 min.Press temperature: 160° C. Replication: 4 per glue *20 min for NR60D-WH

The prepared plywood panels are tested for shear strength under both dryand 48 hour soaked conditions. Twenty OSB panels were manufactured usingthe five resins (4 NR-based resins and one control). The panels weretested right after pressing, without conditioning. Specimens are testedto failure by tension in the dry condition (average 10 specimens). Thetest results are presented in Table 7

TABLE 7 Summary of Plywood Panel Test Results* Press Time Shear Strength(MPa) Glue (min) Dry Test Commercial 3 3.831 (0.537) Plywood 4 4.030(0.523) Adhesive 5 2.732 (0.425) 7 3.692 (0.280) Avg. 3.571 (0.576)MNRP-1H70 3 3.415 (0.182) 4 3.586 (0.169) 5 3.782 (0.354) 7 3.736(0.447) Avg. 3.629 (0.166) MNRP-2H70 3 3.503 (0.201) 4 3.932 (0.314) 53.129 (0.252) 7 2.970 (0.334) Avg. 3.384 (0.429) NR60D-2H 3 2.697(0.208) 4 2.799 (0.192) 5 3.254 (0.239) 7 2.624 (0.208) Avg. 2.843(0.283) NR60D-WH 3 3.111 (0.270) 4 3.041 (0.296) 5 3.347 (0.379) 7 3.515(0.305) Avg. 3.254 (0.218) NR60D-WH** 3 3.761 (0.490) 7 2.836 (0.193)Avg. 3.298 (0.655) *Values in parentheses are standard deviations.**Open assembly time was 20 min for the panels made with this glue,which was the time interval between applying adhesive on the veneers andclosing them together before bonding.

The dry shear strength of the NR-based resins are comparable to thecommercial adhesive bonded panel, and all panels meet the minimum shearstrength of 2.5 MPa required under CSA standard 0112.6-M1977. TheNR-based resins have a lower viscosity and alkalinity, and the adhesivemay easily penetrate into the veneer and starve the glue joint.Optimization of the penetrating property of these resins will increasebonding strength and associated properties.

These results indicate that a substantial proportion of phenol within PFresin formulations may be replaced with an NR fraction obtained frombio-oil for the preparation of adhesives for use in plywood manufacture.

Example 5

Testing of NR60D-2H with PF Adhesives

A) NR60D-2H at 10 and 20%

Eleven 3′×3′×0.5″ plywood panels are manufactured in order to evaluatethe effects of varying concentrations NR60D-2H substitution for phenolin PF resin.

Plywood Panel Manufacture

Blending and Forming

Three different resin compositions are applied to pine veneers (Table8). This resulted in three groups with a minimum of three panels pergroup. All applications are made at a 35 lb/1000 ft² loading rate. Allresins are applied using a plywood glue spreader and applied on a singleglue line.

Billet lay-up for each panel consists of four plies. The face plies arelaid-up parallel to the machine direction and the core plies are laid-upperpendicular to machine direction. Three control panels, fourPF/NR60D-2H, at 10% panels (Group NR60-10%), and four PF/NR60D-2H at 20%(Group NR60-20%) panels are manufactured in the trial.

TABLE 8 Pressing No of Time Group ID Panels Resin Type Resin Loading(sec) Control 3 GP PF Resin 35 lbs/1000 ft² single 300 (Control) glueline NR60-10% 4 GP PF/NR 10 35 lbs/1000 ft² single 300 Resin glue lineNR60-20% 4 GP PF/NR 20 35 lbs/1000 ft² single 300 Resin glue line

Pressing and Testing:

Before pressing, the billets are pre-pressed (cold) at 150 psi for fourminutes in a 4′×8′ press. The panels are then transferred for hotpressing to a 3′×3′ press. The panels are pressed under constantpressure control for 300 seconds at 300° F. Pressing is monitored andcontrolled with a PressMAN© Press Monitoring System. After pressing, thepanels are trimmed to 28″×28″ dimensions and hot stacked. Once cooled,the panels are evaluated. The panels are tested for plywood glue bondand flexural creep (CSA standard 0151-M1978).

No resin quality differences are noted visually during panelmanufacture. The control and NR substituted resins behaved in the samemanner with equal spreadability. The shear data indicates the NRsubstituted resin performed as well as the control (Table 9). TheNR60D-2H (10%) and NR60D-2H (20%) resins both performed comparably tothe control, under both test conditions with respect to shear strength.The resins showed exemplary strength characteristics with the ply onlyfailing on the glue bond a maximum of 12% (PG2-88% average wood failure)under both test conditions. The strength of the NR-resin data is furthersupported by the fact not one sample demonstrated less than 60%, or lessthan 30%, wood failure under both test conditions.

TABLE 9 Test data summary using NR-based plywood shear tests with bothNR60D-2H (105) and NR60D-2H (20%) (Average values for ten specimens perpanel from 3 panels per group) NR Test CSA 0151 60 NR60 ConditionProperty Requirement Units Control 10% 20% Vacuum- Shear Strength No.Req. psi 89 102 88 Pressure Percent Wood 80 % 95 90 88 Soak: FailureAverage Percent Wood 90 % 100 100 100 Failure ≧ 60 Percent Wood 95 % 100100 100 Failure ≧ 30 Boil-Dry Shear Strength No. Req. psi 79 80 69 Boil:Percent Wood 80 % 91 90 91 Failure - Average Percent Wood 90 % 93 100100 Failure ≧ 60 Percent Wood 95 % 100 100 100 Failure ≧ 30B) NR60D-2H used at 25% for the Preparation of Plywood and OSB Panels

A total of seventeen 3′×3′×0.50″ OSB, and fifteen 3′×3′×0.50″ plywoodpanels were manufactured to evaluate the effects of 25% substitution ofNR60D-2H for phenol in PF resin, for both OSB and plywood.

OSB Panel Manufacture

Blending and Forming:

The resins are supplied by Neste in the following formats: Neste PF facecontrol #1, Neste PF core control #2 and Neste PF/NR-60-25%(experimental). Three groups of panels are manufactured as indicated inTable 10. The control group (SNC) consists of the Neste face control #1resin applied to the strands along with commercial E-wax; the strandsare then formed into random homogenous mats. The first experimentalgroup (SNE) consists of the substitution of the Neste PF/NR60-25% resinfor the face control resin in the same manufacturing methodology. Thefinal experimental OSB group (SN) utilizes Neste PF/NR 60-25% on thepanel face strands and the Neste core control #2 on the panel corestrands. The SN mats are of 50/50 face-core random construction.

TABLE 10 PF AND PF-NR60 RESIN OSB TESTS PANEL SPECIFICATIONS Group No.of Thickness Density ID Panels Resin Content Construction (in.) (lb/ft³)Comments SNC 8 Neste PF Face Homogenous 0.5 39 OSB control resin, 3.5%(Control #1) SNE* 6 Neste PF/NR 25, Homogenous 0.5 39 OSB Trial 3.5%SN** 3 Face: Neste 50/50 face- 0.5 39 Face NR PF/NR 25, 3.5% coreSubstitute Core: Neste PF Core Control core resin, 3.5% on OSB (Control#2) *NR/RF resin used on the surface and core of the OSB **NR/PF resinused on surface only

All resins are applied at a 3.5% solids basis. The commercial e-wax isapplied at a 1.0% solids basis. All billets are hand formed to yield adensity of 39 lb/ft³ when pressed to a thickness of 0.5″.

After formation, the mats are then pressed utilizing a standard OSBpressing cycle. The total pressing time is set to a conservative400-second cycle to ensure complete cure of the applied resin. Pressingis monitored and controlled with a PressMAN© Press Monitoring System.

After pressing, the panels arere removed, trimmed to 28″×28″ dimensions,and measured for out-of-press thickness and density and the panels arehot-stacked. Upon cooling, the panels are tested (CSA Standard0437.2-93) for: MOR/MOE, IB, bond durability (2 hr and 6 hr cycles),thickness swell (24 hr soak), and linear expansion (ODVPS) as well asflexural creep.

Plywood Panel Manufacture

Glue Spreading and Veneer Lay Up

Two plywood resins are used for the study. The first resin is Neste PF(plywood control) while the second is Neste PF/NR 25 (plywoodexperimental). The veneer used for plywood manufacture is pine.

The resins are applied to the veneers using a glue spreader. A rate of35 lbs.per 100 ft², applied on a single glue line is utilized. The layup consisted of two face veneers, parallel to machine direction, and twocore veneers, perpendicular to machine direction, for each panel. Elevencontrol (Group PNC) and four experimental (Group PNE) panels, aremanufactured (Table 11).

TABLE 11 PF AND NR60D-2H at 20% RESIN PLYWOOD SHEAR TESTS No. of PANELSPECIFICATIONS Group ID Panels Resin Content Construction Thickness(in.) Comments PNC Control 11 35 lb/m SGL Neste Four ply pine 0.5Plywood PF (plywood) Veneers control PNE 4 35 lb/m SGL Neste Four plypine 0.5 Plywood test (NR-25%) PF/NR (plywood) Veneers resin

During lay up, gluing time, open assembly time, pre-pressing time andclosed assembly time were measured for each panel.

Pressing and Testing

After pre-pressing at four minutes and 150 psi, the billets are placedin a press for final cure and pressing. The first seven control panels(PNC 1-7) are used to establish the pressing time. This resulted in theestablishment of 300 seconds as the required pressing time. Pressing ismonitored and controlled via a PressMAN© Press Monitoring System.

After pressing, the panels are then trimmed to 28″×28″ dimensions andhot stacked. Upon cooling, the panels are evaluated. Testing consistedof glue-bond shear and flexural creep evaluation.

Virtually no difference is observed between the control and NRsubstitution resins. Color, viscosity and spreadability for all resinsis equal, and all resins behave equally in a manufacturing situation.

A comparison of the NR substituted resins versus the control (SN, SNE,vs. SNC) shows bending and bond properties to be equal between the threegroups (Table 12). The results indicate, especially with group SN, adrop in bond durability and linear expansion versus the control. GroupSN showed a value of water swell well within the maximum requirement(data not included)

TABLE 12 SUMMARY OF PF AND PF/NR60 at 25% OSB TESTS NR NR ControlSurface/ Surface/NR Group Neste Core Core Property Req Units (SNC) (SN)*(SNE**) Modulus of Rupture Min. psi 3210 3190 3190 (after pre- 2500conditioning) Modulus of Min. psi × 479 493 469 Elasticity (after 4501000 pre-conditioning) Internal Bond (after Min. psi 56.3 49.7 54.6pre-conditioning) 50.0 Bond Durability: MOR after 2 HR. Min. psi 1.8e+0713101550 14201870 BOIL (tested 1250 when wet) MOR after 6 cycle Min. psi1250 *NR/PF resin used on surface only **NR/RF resin used on the surfaceand core of the OSB

With respect to the plywood shear testing the results are favourableboth against the standard and the control Group (Table 13). A strongbond is indicated by the shear strength performance under both testconditions. Under both conditions 11% or less failure could beattributed to the glue while the maximum allowable is 20% (89% woodfailure for Group PNE under boil-dry-boil). A further indicator in thestrength of the data is that not one PNE sample showed wood failurevalues of less than 60% or 30% under both test conditions (100% pass forboth requirements on both test regimens).

TABLE 13 SUMMARY OF PF AND PF/NR60 at 25% RESIN PLYWOOD SHEAR TESTSControl Test CSA 0151 Group Neste NR/PF Condition Property RequirementUnits (PNC) (PNE) Vacuum- Shear Strength No. Req. psi 82 110 PressurePercent Wood 80 % 87 93 Soak: Failure Average Percent Wood 90 % 93 100Failure ≧ 60 Percent Wood 95 % 100 100 Failure ≧ 30 Boil-Dry ShearStrength No. Req. psi 74 83 Boil: Percent Wood 80 % 89 89 FailureAverage Percent Wood 90 % 100 100 Failure ≧ 60 Percent Wood 95 % 100 100Failure ≧ 30

Example 6

OSB Testing of NR-60 and MNRP

Further tests were carried out at W.K.I. in Germany to assess theindustrial performance of NR-containing resins against a commercial PFOSB resin. Control resins, and resins having from 20% to 50% phenolsubstitution of either NR-60 or MNRP were manufactured and used fortesting. Testing of the OSB boards were compared against EuropeanStandards for test protocols including V100, EN 300/1997, typically atthree press cycles in the range of 12-16 s/mm.

Boards were tested according to EN 300/1997 and particularly for Type 4OSB, for heavy duty load-bearing. Further to the V100 value, the option2 V100 test (conducted after the boiled samples were dried) was alsocarried out.

NR-60

The properties of the NR-60 at 30%, and control resins, and the resultsof the W.K.I. board tests are given in Table 14.

TABLE 14 Resin specifications, and Properties of the OSB samples usingNR-60 at 30% substitution Control NR-60 Resin # % substitution — 30%Molar ratio 2.10 1.87 NaOH, % 6.0 7.4 Solids 2 h @ 120° C. 42.1 53.5Viscosity, cp 370 350 Alkalinity test, % 5.92 6.31 Properties of OSBDensity, kg/m 661 681 IB, N/mm² 0.55 0.55 V100, N/mm² 0.24 0.24 V100option 2, N/mm² 0.44 0.52 MOR, N/mm² 23.7 23.9 MOR after boiling 10.810.5 24 h swells, % 19.4 18.0 HCHO, mg 1.19 1.11 Moisture, % 4.27 5.29

These results indicate that the NR-60 performed at least as well as thecontrol, while the V100 Option 2 values and swells were improved whencompared to the control. The results from the OSB trial were successfuland they confirmed results obtained in the lab.

Repeated trials using NR-60 based resins at 30% substitution, and OSBmade using this resin are present in Table 15.

TABLE 15 Resin specifications, and Properties of the OSB samples usingNR-60 at 30% substitution Control NR-60 Resin # % substitution — 30%Molar ratio 2.10 1.84 NaOH, % 6.0 7.4 Solids 2 h @ 120° C. 42.1 43.2Viscosity, cp 370 340 Alkalinity test, % 5.92 6.36 Properties of OSB: 12s/mm press cycle Density, kg/m 722 726 IB, N/mm² 0.61 0.81 V100, N/mm²0.19 0.27 24 h swells, % 16.5 13.7 Properties of OSB: 14 s/mm presscycle Density, kg/m 728 722 IB, N/mm² 0.82 0.92 V100 0.29 0.33 24 hswells, % 14.1 16.1 HCHO, mg 2.8 1.7 Moisture, % 8.1 7.9 Properties ofOSB: 16 s/mm press cycle Density, kg/m 734 724 IB, N/mm² 0.93 0.94 V1000.34 0.37 24 h swells, % 14.5 14.4

These results demonstrate that the properties of the OSB made usingNR-60 resins exceeded those of the control resin. The use of NR-60 at30% of phenol indicates that the effectiveness of the phenolic resin wasequal or even better than the respective ones of the control; all wetproperties seemed unchanged, while the (free) formaldehyde release wassubstantially reduced. Furthermore, these results demonstrate that theNR-60 product is consistent when produced at different times, fromdifferent NR60-D batches, and used in independent trials.

A second series of NR resins were prepared using standard NR-60 productsto substitute up to 40% of the phenol. These NR-60 substituted resinsand the OSB made using these resins are compared to a control resin inTable 16.

TABLE 16 Resin specifications, and Properties of the OSB samples usingNR-60 at 40% substitution Control NR-60 Control* NR-60* Resin # %substitution — 40% — 40 Molar ratio 2.10 2.04 2.10 1.50 NaOH, % 6.107.40 6.1 7.4 Solids 2 h @ 120° C. 42.2 44.0 42.0 43.3 Viscosity, cp 380340 320 330 Alkalinity test, % 6.18 6.54 5.50 5.95 Properties of OSB: 12s/mm press cycle Density, kg/m 719 716 714 722 IB, N/mm² 0.58 0.50 0.830.66 V100, N/mm² 0.20 0.12 0.36 0.35 24 h swells, % 17.6 19.0 14.7 15.5Properties of OSB: 14 s/mm press cycle Density, kg/m 736 726 725 730 IB,N/mm² 0.71 0.73 0.92 0.93 V100, N/mm² 0.30 0.24 0.39 0.35 24 h swells, %17.4 17.6 14.7 14.2 MOR before 25.2 23.5 24.6 21.2 after boiling 7.4 5.96.7 5.6 HCHO, mg 2.4 1.3 3.2 0.8 Moisture, % 8.4 8.4 8.3 8.3 Propertiesof OSB: 16 s/mm press cycle Density, kg/m 742 727 726 726 IB, N/mm² 0.650.65 1.01 0.94 V100 0.34 0.20 0.43 0.32 24 h swells, % 17.4 19.6 15.715.3 *separate trail using different NR-60

Collectively the results in Table 16 demonstrate that, both dry and wet,the properties of the NR-60 OSB at 40% phenol substitution exceededthose of the OSB boards produced with the commercial PF resin (control).The free formaldehyde of NR-60 boards was lower than that of thecontrol. In general, the OSB board properties of the NR-60 based resinmet or exceeded the control resin board properties, and the boardproperties of the NR-60 resin met or exceeded most of the control resinOSB board properties. Furthermore, batch-to-batch consistency of NR-60is observed since both NR-60 based resins performed equally as well.

MNRP

Resins comprising 20, 40 and 50% MNRP substitution, in place of phenolwere also evaluated, and the results are presented in Tables 17, 18 and19, respectively.

TABLE 17 Resin specifications and Properties of the OSB samples usingMNRP at 20% substitution Control MNRP Resin # % substitution — 20% Molarratio 2.10 2.14 NaOH, % 6.10 6.55 Solids 2 h @ 120° C. 42.1 41.5Viscosity, cp 360 370 Alkalinity test, % 5.67 5.53 Properties or OSB: 12s/mm press cycle Density, kg/m 726 737 IB, N/mm² 0.68 1.03 V100, N/mm²0.26 0.37 24 h swells, % 14.9 13.3 Properties of OSB: 14 s/mm presscycle Density, kg/m 726 733 IB, N/mm² 0.61 0.75 V100, N/mm² 0.25 0.27 24h swells, % 16.6 13.9 MOR, N/mm² 23.9 25.3 MOR retention, % 27.6 23.4HCHO, mg/100 gm 2.5 1.4 Moisture, % 8.0 8.0 Properties of OSB: 16 s/mmpress cycle Density, kg/m 734 737 IB, N/mm² 0.95 0.79 V100, N/mm² 0.350.25 24 h swells, % 15.5 14.4

TABLE 18 Resin specifications, and Properties of the OSB samples usingMNRP at 40% substitution Control MNRP MNRP Resin # % substitution — 40%40% Molar ratio 2.10 2.10 2.10 NaOH, % 6.10 7.65 7.6 Solids 2 h @ 120°C. 42.0 44.3 43.4 Viscosity, cp 320 340 320 Alkalinity test, % 5.50 6.446.28 Properties of OSB: 12 s/mm press cycle Density, kg/m 714 733 725IB, N/mm² 0.83 0.78 0.77 V100, N/mm² 0.36 0.32 0.27 24 h swells, % 14.716.8 17.4 Properties of OSB: 14 s/mm press cycle Density, kg/m 725 742730 IB, N/mm² 0.92 1.01 0.91 V100, N/mm² 0.39 0.28 0.35 24 h swells, %14.7 16.5 14.4 MOR, before 24.6 23.7 24.0 MOR, after boiling 6.76 5.85.6 HCHO, mg 3.2 1.8 2.0 Moisture, % 8.3 8.1 7.8 Properties of OSB: 16s/mm press cycle Density, kg/m 726 728 730 IB, N/mm² 1.01 0.98 0.96V100, N/mm² 0.43 0.34 0.37 24 h swells, % 15.7 17.0 16.5

TABLE 19 Resin specifications, and Properties of the OSB samples usingMNRP at 50% substitution Control MNRP Resin # % substitution — 50% Molarratio 2.10 2.10 NaOH, % 6.10 7.55 Solids 2 h @ 120° C. 42.0 43.5Viscosity, cp 475 350 Alkalinity test, % 5.50 5.55 Properties of OSB: 12s/mm press cycle Density, kg/m 724 718 IB, N/mm² 0.99 0.61 V100, N/mm²0.36 0.18 24 h swells, % 14.8 17.6 Properties of OSB: 14 s/mm presscycle Density, kg/m 729 726 m, N/mm² 0.98 0.76 24 h swells, % 15.0 16.3MOR, before boiling 22.8 24.2 MOR, after boiling 7.2 4.6 HCHO, mg 3.31.6 Moisture, % 8.1 8.6 Properties of OSB: 16 s/mm press cycle Density,kg/m 747 728 IB, N/mm² 1.03 0.84 V100, N/mm² 0.43 0.28 24 h swells, %16.3 16.5

These results indicate that the MNRP-based resin is as or more reactivethan the control resin, since the best results were obtained at shortestpress cycle. It is also notable that the swelling values are low. At 40%substitution MNRP produced OSB boards that were comparable to controlOSB boards even at short press cycles. At 50% substitution with MNRP,the board properties were reduced as compared to the control's, andlonger press cycles were required to achieve satisfactory results.

Example 7

Analysis of MNRP Based Resin

A set of panels 28″×28″ were prepared using strands from Ainsworth orDraytion Valley AB. A core and surface resin were used for thepreparation of the pannels. The core resin was MDI (Rubinate 1840), andthe surface resin was either a control (commercial) or MNRP resin at theconcentrations listied in Table 20.

TABLE 20 Resins used for panel preparation. PF Resin Urea SolidsViscosity Alkalinity Panel Set % % cp @ 25° C. % 2 ACM control 7.0 49.9160 3.18 3 MNRP 30% 4.8 45.0 250 6.50 4 MNRP 30% 6.8 52.5 160 3.50 5Ainsworth control — — — — 7 MNRP 50% 7.0 53.2 150 3.63 8 MNRP 30% 12.051.4 175 3.46

The panels were prepared having a wax content of 1.0%, using randomorientation of strands (face/core 55/45), with a target thickness of7/16″, press temperature of 400° F., and press closing 30 sec. Panelswere tested for Modulus of Rupture, Modulus of elasticity, Internal Bond(all CSA 0437), Thickness swell, Water Absorption and Edge Swell. Theresults are presented in Table 21.

TABLE 21 Analysis of OSB prepared using resins and panel sets defined inTable 20 Panel Set 2 3-1* 3-2* 4* 5 7* 8* Density, kg/m³ 609 622 618 634615 640 603 Hot IB, N/mm² 0.352 0.407 0.388 0.381 0.392 0.272 0.359 IBdry, N/mm² 0.267 0.300 0.329 0.386 0.268 0.341 0.207 IB wet, N/mm² 0.0220.042 0.024 0.033 0.024 0.015 0.028 MOR dry, N/mm² 16.94 35.71 19.0526.05 19.32 11.31 27.71 MOR wet, N/mm² 5.67 6.45 6.08 5.57 4.28 2.745.51 MOE dry N/mm² 2728.2 3566.4 2606.1 3297.3 3553.5 2246.1 4223.7 MOEwet N/mm² 660.4 679.4 647.0 546.5 491.5 302.1 542.6 Swells, %, ** 28.1325.08 26.56 30.94 26.09 30.62 19.29 % after wet test 44.7 40.2 47.5 43.547.2 46.5 45.6 *MNRP resin ** at 24 h at 20° C.These results indicate that MNRP substituted resins, at either 30 or 50%produce OSBs that perform as well or better than those of the controlresin formulations.

All citations are herein incorporated by reference.

The present invention has been described with regard to preferredembodiments. However, it will be obvious to persons skilled in the artthat a number of variations and modifications can be made withoutdeparting from the scope of the invention as described herein.

References

-   Chum et al., 1989, ACS Symposium Series No. 385, Adhesives from    Renewable Resources, Hemingway R. W. Conner A. H. eds, American    Chemical Society, pp. 135-151.-   Forss K. G., Fuhrmann, A. 1979 Finnish plywood, particle board, and    fibreboard made with a lignin-based adhesive. Forest Prod. J. vol    29, pp. 39-43.-   Himmelblau D. A., Grozdits G. A. 1997, Production of wood composite    adhesives with air-blown, fluidized-bed pyrolysis oil.-   Kelley et al., 1997, Use of Biomass pyrolysis oils for preparation    of modified phenol formaldehyde resins, Vol 1 pp. 557-172-   Pakdel, H., Amen-Chen, C., Zhang, J., Roy, C. 1996, Phenolic    compounds from vacuum pyrolysis of biomass, pp. 124-131, CPL press-   Scott 1988, Chemicals and fuels from biomass flash pyrolysis—part of    the bioenergy development program, Renewable Energy Branch, Energy    Mines and Resources Canada, Ottawa, Canada, DSS Contract File No.    38ST 23216-6-65164;-   Sellers 1996; Adhesives Age vol 39: pp. 6-9-   White 1995; Forest Prod J. vol 45, pp.21-28

1. A natural resin (NR) characterized by comprising: i) a phenol contentfrom about 0.001% to about 0.1% (w/w); ii) a total phenolic content fromabout 35% to about 95% (w/w); iii) a smoky odour; iv) a pH from about2.0 to about 5.0; v) a water content of from about 1 to about 10 wt %;vi) an acids content of from about 0.1 to about 5.0 dry wt %; and vii)an average molecular weight (wet)/(dry) of from about(300-450)/(350-500) Daltons; wherein the NR is solid at roomtemperature.
 2. The NR of claim 1 further characterized by comprising i)a water content of from about 3 to about 10 wt %, and a melting pointfrom about 70° C. to about 150° C.
 3. The NR of claim 1 furthercharacterized by comprising: i) a net calorie value of about 4355 cal/g(18.22 MJ/kg); and ii) a gross calorie value of about 4690 cal/g (19.62MJ/kg).
 4. A resin composition comprising the NR of claim
 1. 5. Theresin composition of claim 4 wherein said resin is an adhesive resin,and said NR is present within said resin composition from about 1% toabout 40% (w/w).
 6. The resin composition of claim 4, comprising aphenol formaldehyde resin, wherein a portion of the formaldehyde of saidphenol-containing formaldehyde resin is replaced with NR.
 7. The resincomposition of claim 6 wherein NR replaces up to about 50% of saidformaldehyde content within said phenol-containing formaldehyde resin.8. The resin composition of claim 7 comprising a formaldehyde:phenolfrom about 1.2:1 to about 3:1.
 9. The resin composition of claim 8wherein the formaldehyde:phenol ratio is 1.6:1.
 10. The resincomposition of claim 4, comprising a phenol formaldehyde resin, whereinup to about 100% of the phenol content, of said phenol-containingformaldehyde resin is replaced with NR.
 11. A product prepared using theresin composition of claim
 4. 12. A product prepared using the resincomposition of claim
 5. 13. A product prepared using the resincomposition of claim
 6. 14. The product of claim 11 comprising, anindustrial resin product.
 15. The product of claim 14, wherein saidindustrial resin product is selected from the group consisting oflaminated wood, plywood, particle board, high density particle board,oriented strand board, medium density fiber board, hardboard or waferboard, mouldings, linings, insulation, foundry resins, asphalt,concrete, brake linings and grit binders.
 16. A method of preparing asolid natural resin (NR) comprising: i) liquefying wood, wood bark orother biomass using fast pyrolysis in order to produce vapours and char;ii) removing said char from said vapours; iii) recovering said vapoursto obtain a liquid product; and iv) processing said liquid product usingdistillation/evaporation to produce said solid NR.
 17. The method ofclaim 16 wherein, said step of recovering comprises obtaining saidliquid product from a primary recovery unit, a secondary recovery unitor both a primary and a secondary recovery unit.
 18. The method of claim17 wherein said step of processing comprises pretreating said liquidproduct prior to said distillation/evaporation.
 19. The method of claim18 wherein said pretreating comprises adding water to said liquidproduct prior to said distillation/evaporation.
 20. The method of claim16 wherein said step of processing further comprises adding water tosaid NR obtained following distillation/evaporation.
 21. A natural resinprepared according to the method of claim
 16. 22. A resin compositioncomprising the a natural resin (NR) prepared according to the method of:i) liquefying wood, wood bark or other biomass using fast pyrolysis inorder to produce vapours and char; ii) removing said char from saidvapours; iii) recovering said vapours to obtain a liquid product; andiv) processing said liquid product using distillation/evaporation toproduce said NR.
 23. The resin composition of claim 22 wherein saidresin composition is an adhesive composition.
 24. An industrial productprepared using the adhesive composition of claim
 23. 25. The product ofclaim 24, wherein said industrial resin product is selected from thegroup consisting of laminated wood, plywood, particle board, highdensity particle board, oriented strand board, medium density fiberboard, hardboard or wafer board, mouldings, linings, insulation, foundryresins, asphalt, concrete, brake linings, and grit binder.
 26. The NR ofclaim 1 further characterized by comprising: (a) a water content ofabout 6 wt %; (b) a pH of about 2.5; (c) an acid content of about 0.7dry wt %; and (d) an NRP index of about
 90. 27. The NR of claim 26,further characterized by comprising an average molecular weight of about388/412 (wet/dry).
 28. The NR of claim 1, further characterized bycomprising a melting point from about 110° to about 150° C.
 29. The NRof claim 28 comprising: (a) a phenolic content of about 95%; (b) ahydrocarbon content of about 0.1%; (c) an acids content of about 1%; (d)a water content of about 3%; and (e) a total ester, aldehyde and alcoholcontent of about 0.9%.
 30. The NR of claim 29 further characterized bycomprising: (a) gasoline solubility of about 1%; (b) an ash content ofabout 0.01%; (c) a flash point of greater than about 280° C.; (d) adensity of about 1.19 g/cm3 at 25° C.; (e) a hydroxyl content of about1.4%; and (f) a methoxyl content of about 5.3%.